Perspectives On The Synthesis of Organic Carbamates

Tetrahedron 68 (2012) 15e45
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Tetrahedron report number 958
Perspectives on the synthesis of organic carbamates

Devdutt Chaturvedi *
Natural Products Chemistry Division, North-East Institute of Science and Technology (CSIR), Jorhat 785006, Assam, India
a r t i c l e i n f o
Article history:
Received 6 September 2011
Available online 6 October 2011
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16
Classification of carbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17
Methods of preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17
3.1.
Phosgenation technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.
Reductive carbonylation of nitroaromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3.
Oxidative carbonylation of amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.4.
Using metal/non-metal carbonates/bicarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.5.
Synthesis of carbamates using carbon dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.5.1.
Gaseous carbon dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.5.2.
Electrochemical carbon dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.5.3.
Supercritical carbon dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.5.4.
Organic carbonates with carbon dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.6.
Carbamate synthesis from dithiocompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.6.1.
Using dithiocarbamates/thiocarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.6.2.
From carbon-imido dithiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.7.
Carbamate synthesis through rearrangement reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.7.1.
Hoffmann rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.7.2.
Curtius rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.7.3.
Lossen rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.8.
Miscellaneous methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.8.1.
Carbamate synthesis using carbonyl di-imidazole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.8.2.
Carbamate synthesis using sodium cyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.8.3.
Carbamates synthesis using Burgess reagent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.8.4.
Carbamate synthesis through transcarbamoylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.8.5.
Carbamate synthesis using ureas and alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.8.6.
Carbamate synthesis from carbonyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.8.7.
Carbamate synthesis from oximes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
References and notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Biographical sketch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
* Corresponding author. Fax: 91 376 2370011; e-mail addresses: ddchaturvedi@rrljorhat.res.in, devduttchaturvedi@gmail.com.

0040-4020/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.10.001
16
D. Chaturvedi / Tetrahedron 68 (2012) 15e45
anti-HIV, antiestrogenic, antiprogestational, antiosteoporosis, antiinammatory, antilarial, antitubercular, antidiabetic, antiobesity,

anticonvulsant, antihelminthes, anti-alzheimer drugs and CNS and
CVS active agents (Fig. 1).5c,d,14
Some of the recent molecules in which the extensive role of
incorporation of carbamates have been studied are discodermolide,15 camptothecin16 podophyllotoxin,17 mitomycins,18
vitamin-D3,19 geldanamycin,20 fumagillin analogues,21 butelinic
acid,22 amphotericin-B,23 cephalosporins,24 doxorubicin,25 rapamycin,26 anisomycin,27 quiniclidine,28 phytostigmine,29 novobiocin,30 oestradiol,31 cholesterol,32 sphingomyelin,33 vancomycin,34
marphinan,35 rifampicin,36 vulmbactin,37 pregnelone,38 himbacine,39 iejimalides,40 rhazinilam,41 maytansine,42 calcheamycin,13c
combretastanin,43 cyclosporin,44 duocarmycins45 etc. Beside the
above mentioned molecules, several kinds of other structurally
diverse natural/synthetic molecules have also been reported in the
recent years wherein carbamates play crucial role in improving the
biological activity prole than the parent molecules. Some of the
important potential carbamates derivatives of structurally diverse
biologically active anticancer,19,46 antibacterial,5e,47 antimalarial,48
antidiabetic,49 antioxidant,50 antiinamatory,51 antitubercular,52
antiprogestational,53 anti-HIV,17 anticougulant,54 antiestrogenic,55
CNS-active,28 are depicted in Figs. 2e5, respectively. Several of
natural, semisynthetic, synthetic lead molecules bearing carbamate
functionality have been discovered in recent past and are in the
various phases of drug development.5,12a,13,56
Although, some of the review articles on the different aspects on
the chemistry of organic carbamates have been published but the
review articles dealing synthetic aspects of the carbamates were
only published long back.1a,2aed Furthermore, till now there is no
recent review published since more than 3 decades, which could
cover the synthetic aspects of the organic carbamates. Since last
2e3 decades, much progress on the synthesis of organic carbamates has been realised, employing various kinds of cheap and safe
alternatives, such as various forms of carbon dioxide, organic
1. Introduction
Organic carbamates are a stable class of compounds derived
from the unstable carbamic acid (H2NeCOOH) by substitution of
the amino and carboxyl moieties with various kinds of structurally
diverse alkyl/aryl, aryl/alkyl or substituted alkyl/aryl and aryl/alkyl
groups, and are identied by the presence of the linkage
OeCOeNHe.1,2 When the carbamate linkage is present in a cyclic
system, this class of compounds are referred to as cyclic carbamates.3 When the carbamate group is attached to any inorganic
atom, either metallic or nonmetallic, such compounds are referred
to as inorganic carbamates.4
Organic carbamates represent an important class of compounds
showing various interesting properties. They nd wide utility in
areas, such as pharmaceuticals,5 agrochemicals6 (pesticides, herbicides, insecticides, fungicides etc.), as intermediates in organic
synthesis,7 for the protection of amino groups in peptide chemistry,8 and as linkers in combinatorial chemistry.9 Functionalisation
of amines as carbamates offers an attractive method for the generation of derivatives, which may have interesting medicinal and
biological properties.10 Organic carbamates have been extensively
used as intermediate for the synthesis of structurally diverse synthetic intermediates/molecules of biological signicance.11 Therefore, considerable interest has been generated in the recent past in
the development of efcient and safe methodologies for carbamate
ester synthesis.
Organic carbamates have frequently been employed as pharmaceuticals in the forms of drugs and prodrugs.5a,12a In recent
years, several reports have indicated that the carbamate linkage
present in the active pharmacophores of various structurally diverse molecules increases the biological activities of semisynthetic/
synthetic natural/synthetic molecules.13 Furthermore, the role of
the carbamate linkage has been extensively studied in structurally
diverse natural/semisynthetic molecules against various diseases,
such as anticancer, antibacterial, antifungal, antimalarial, antiviral,
O
OH O
O
NH
OH
H3CHN
O
OH
OH O
AcO
Physostigmine: Anti-alzheimer drug

O
Taxol analogues: anticancer drugs

O
N
Cl
NH
Linezolid: Antibacterial drug
NH2
Cl
Capravirine: anti-HIV
O
O
NHCH3
O
Carbaryl: Insecticide
O HO
Telithromycin: Antibacterial drug
Fig. 1. Biologically active drug molecules bearing carbamate linkage.
17
O
O
O
O
O
HN
NH2
OMe
MeO
H2N
OH
O
NH
PPI-2458
MeO
O
Geldanamycin
OH
OH
O
O
O
HN
HN
OH
Vitamin D3 carbamate dimer

O
H
N
O
O
OMe
R
MeO
N
H
CH3
O
NH
NH
Staurosporine derivatives
Podophyllotoxin analogues
Fig. 2. Potential anticancer carbamates of various natural products.
carbonates and several other useful synthetic routes. Thus, keeping

the above views under considerations this review has been planned
to deal on the various synthetic aspects of organic carbamates with
the special emphasis on the recent methodologies.
triphosgene, which is relatively safer to use.60 Thus, carbamate 6

synthesis has been achieved through the reaction of an amine 4
with an alcohol 5 using either 1, or 2 or 3 as the source of a carbonyl
equivalent (Scheme 1).
2. Classication of carbamates
Cl
Cl
Carbamates can be mainly classied into two groups, namely

inorganic and organic. Depending upon the structural variations in
the attached moieties, they are further classied as shown in Fig. 6.
Cl
Cl
Cl
Cl
Cl
Cl
Phosgene (1) is a potentially useful, versatile building block in

organic synthesis.57 It offers the possibility of binding two nucleophilic units to the same carbon atom and this two-component
system is particularly well suited for the combinatorial synthesis
of carbonates, ureas and carbamates (Scheme 1). Phosgene is,
however, extremely toxic, which limits its use. Safer substitutes
have been proposed, such as 1,1,1-trichloromethylformate (diphosgene 2),58 and bis-(1,1,1-trichloromethyl) carbonate (triphosgene 3),59 which have been frequently used in recent years.
Depolymerisation of 3 into 1 has widely replaced phosgene by
Cl
R1NH2 +
4
+ R2OH
5
(either 1 or 2 or 3)
X
Cl
O
Cl
3
O
3. Methods of preparation
3.1. Phosgenation technique
Cl
NHR1
OR2
Scheme 1.
Chloroformates and isocyanates are intermediates produced

from phosgene, and have frequently been employed in the synthesis of organic carbamates. Chloroformates57a 7, obtained
through the reaction of alcohols/phenols 5 with phosgene 1, react
with amines/substituted amines 4 (i.e., aminolysis) affording carbamates61 6 (Scheme 2). Carbamate synthesis through the chloroformates route has been achieved using different reaction
18
HO
HO
O
OMe
OMe
N
O
HO
HO
O
NH
O
O
NH
OMe
O
O
Erythromycin derivatives
N
R2
HO
HN
O
HO
OH
OH
O
O
O
HO
O
O
NH
O
NH
O
OMe
R1
O
O
Azithromycin derivatives
HN
O
O
COOH
XAc
Carbamate conjugate of cephalosporin with oxazolidinones

Fig. 3. Potential antibacterial carbamates of various natural products.
Scheme 2.
conditions, such as the use of strong bases8a,62 (NaOH, NaHCO3,

Et3N, pyridine and triphenylphosphine), metals,63 ultrasound,64
bis(trimethylsilyl)acetamide61 and in combination with azides.63
In recent years, there has been much attention focused on the
synthesis of carbamates using chloroformates as key intermediates.
Thus, Pandey and co-workers have reported65 an efcient synthesis
of carbamates 6 through the reaction of variety of amines 4 with
chloroformates 7 using catalytic amount of a yttriaezirconium
based Lewis acid catalyst (Scheme 3).
R1NH2 + ClCOOR2
7
4
O
OH
BTC
Pyr
Cl
O
O
R2O
10
OCH2R2
75-99% R1 NH2
4
O
R2O
NHR1
NHR1
6
Scheme 3.
5
R2OH
Pyr
yttria-zirconia based
Lewis acid catalyst
rt, 5 min-6 h, 88-96%
Later, Mormeneo and co-workers have reported66 a versatile

method for the synthesis of carbamates 6 through an in situ generated, polymer-supported chloroformate resin 9. Bis-(1,1,1trichloromethyl) carbonate (BTC, triphosgene) has been used as
a phosgene equivalent to afford a supported chloroformate 9, which
on sequential one-pot reaction of a variety of alcohols 5 with amines
4 afforded the corresponding carbamates 6 in high yields via 10
(Scheme 4).
Scheme 4.
19
HO
CF3
N
HN
Cl
NH
Antioxidant
Antimalarial
OH
F3C
Cl
HO
N
H
O
NH
O
F
N
H
Antiinflammatory
Antidiabetic
O
F
H
N
Ph
O
COOH
O
O
COOR
Antitubercular
Fig. 4. Biologically potent carbamates of natural/synthetic molecules.
Raje and co-workers have reported67 an efcient, one-pot synthesis of N-substituted (3-oxobutyl) carbamates 12, via tandem
condensation of primary amines 4 with methyl chloroformate 7
(R2Me) followed by conjugate addition of the resulting carbamates with methyl vinyl ketone 11 in the presence of Sn4 modied
zeolite Hb (Hb-SnA) at room temperature (Scheme 5).
O
11
R1NH2 + ClCOOR2
4
7
24 h, 68-75%
R1NCOOR2
12
Scheme 5.
More recently, Kim and Jung have reported68 a simple and efcient synthesis of carbamates 6, through reacting equimolar
amounts of amines 4, chloroformates 7 and indium metal (Scheme
6). Thus, carbamates of structurally diverse substituted aliphatic,
aromatic and heterocyclic amines were prepared using various
kinds of chloroformates.
O
phenols) affording the corresponding carbamates is the most

common way to synthesise carbamates (Scheme 7).70 Polyurethanes,71a the building blocks of isocyanates, have been extensively used in industry. Some of the 12 million tonnes of
polyurethanes are made annually from the reaction between glycols and diisocyanates, and there are currently many papers and
patents on ways to catalyse and control these reactions.71b The
synthesis of carbamates starting from isocyanates could be achieved through the use of strong bases,72 and metal halides73 etc.
Carbamates could be converted into isocyanates by thermal decomposition at higher temperatures using different reaction conditions, such as use of metal catalysts,74 chlorocatecholborane/
boron halides with triethylamine,75 silanes,76 chlorosilanes,77
dichlorosilanes,78 Mitsunobu reaction conditions,79 montmorillonite K-10,80 Bi2O3,81 and very recently basic metal oxide nanoparticles82 etc.
O
+
Cl
Cl
R1NH2
R1-N=C=O
13
+ R2OH
- R2OH
R2O
NHR1
Scheme 7.
In
R1NH2 + Cl
4
OR2
rt, 7-12 h,
73-91%
R2O
NHR1
R2 = - CH3, -CH=CH2, Bn
Scheme 6.
Isocyanates2a,69a 13, obtained through the reaction of phosgene

1 and amines 4, reacts with hydroxy compounds 5 (i.e., alcohol/
3.2. Reductive carbonylation of nitroaromatics

The reductive carbonylation of aromatic nitrocompounds 14 to
the corresponding carbamates is an interesting approach towards
the synthesis of carbamates 15 (Scheme 8).83 The carbonylation
reaction of nitroaromatics is exothermic and is catalysed by palladium, ruthenium, and, to a lesser extent, rhodium. In addition,
platinum,84 iridium85 and iron,86 have been reported to be active in
this reaction.
20
O
Cl
Et
H
N
Cl
Et
NH
O
NH
Antiprogestational
O
O
NH
R2
O
R1
OMe
MeO
CNS-Active
OH
Anti-HIV
O
O
NH
N
H
NH
O
N
N
Anticoagulant
HO
Antiestrogenic
Fig. 5. Biologically potent carbamates of natural/synthetic molecules.
a mechanism using Ru(dppe)(CO)3 17 dppebis(diphenylphosphino)ethane as a catalyst through the involvement of intermediates 18e22,
in which an aromatic amine 4 is suggested as a linker intermediate
(Scheme 10).
Ph2.P
Scheme 8.
For a reductive carbonylation of aromatic nitrocompounds carried out in alcohols, it might generally be considered that the carbamates16 are formed by the reaction of aromatic isocyanates
ArNCO, with an alcohol ReOH, outside the coordination sphere of
the metal.87 However, Cenini has found in the case of Ru3(CO)12
with NEt4Cl as a co-catalyst that the alcohol participates in the
catalytic cycle, since, when it was absent, practically no isocyanate
was obtained (Scheme 9).
+ ArNO2
P.Ph2
-CO2 OC
Ph2.P
O
Ru
N
OC CO
Ar
NH-Ar
LnM
CO
COOR'
OR'
Ar-HN
+ LnMC=O
16
Scheme 9.
Several reports have been published by Gladfelter and Cenini

giving more insight into the mechanism of the catalytic cycle of the
rhodium and ruthenium catalysts. Gladfelter88 has proposed
OC
P.Ph2
O
Ru
-ArNH2
N
CO
Ar
-CO2
O
19
P.Ph2
Ru
CO
OC
17
CO
OMe
OH
22
Ph2.P
+ CO
O
CO, R'OH
Ph2.P
Ru CO
18
Ph2.P
LnM=N-Ar
P.Ph2
P.Ph2
OMe
ArN=C=O
+ArNH2
Ru
Ph2.P
P.Ph2
O
N H
Ar
OC CO
O 21
-MeOH
COOMe
Ru
OC
CO
Ar-CO-NH.Ar
ArNH2
R1NH2
4
COOMe
20
O
Ar-NH
OR'
16
Scheme 10.
21
Carbamates
In o rg a n ic
O rg an ic
Saturated
Non metal
Metal
Unsaturated
Symmetrical Unsymmetrical
Aliphatic
Aromatic
Aliphatic-aromatic
Simple
Others
Substituted
Simple
Activated
Cyclic
Simple
Functional
Imido
Thio
Symmetrical
Pyro
Linear-alicyclic
Alicyclic
Branched
Linear
Ortho
Unsymmetrical
Symmetrical Unsymmetrical
S im p le
S u b s t it u t e d
Fig. 6. Classication of carbamates.
Very similar results were obtained by Cenini using [(PPh3)2N]

[Rh(CO)4] 23 as a catalyst through the involvement of intermediates
24e27(Scheme 11).4d,89
[(PPh3)2N]
Ar-NO2
O=C
[(Rh(CO)4]
23
+ CO, ArNH2
O=C
O=C
COOMe
Rh
Rh
24
O=C
Ar
27
COOMe
+ 2CO & 2MeOH
O=C
+ CO
O
Rh
O=C
O=C
CO2
Rh
Ar
O=C
25
Ar
of the type [Pd(Py)2Cl2] can catalyse the reaction at a low Py/Pd

ratio, but the method requires promotors, such as FeCl3 or MoCl5
and aprotic solvents, such as chlorobenzene.91 On the other hand,
reductive carbonylation of aromatic nitrocompounds could be
catalysed by palladium anchored to montmorillonite,92 supported
Pd-1,10-phenanthroline complexes in the presence of a Brnsted
acid,93 Pd complexes with 1,10-phenanthroline derivatives and Pd
heteropolyanions.94 In addition, ruthenium carbonyl complexes,
such as Ru3(CO)12 or Ru(CO)3(PPh3)2 are efcient homogeneous
catalysts in the reductive carbonylation of aromatic nitrocompounds to carbamates, if additives, such as alkylammonium
salts,95 chelating ligands,96 or anilines97 are used. Palladium98 has
often been applied as a catalyst in homogeneous and heterogeneous systems. Rhodium2d catalysts have also been applied less
often to the reductive carbonylation of nitrobenzene than ruthenium and palladium catalysts.
Chandrasekhar and co-workers have reported64 an efcient
protocol for the synthesis of carbamates 15 through the reductive
carbonylation of aromatic nitrocompounds 14 with either (Boc)2O
28, or ClCOOEt using a Sn/NH4Cl system under ultrasound radiation
(Scheme 12).
26
Scheme 11.
Most previously reported catalytic systems for the reductive

carbonylation of aromatic nitrocompounds have usually employed
corrosive Lewis acids and/or a base,90 such as pyridine or triethylamine in excess amounts, e.g., supported palladium is inactive in
the absence of a Lewis acid, even in the presence of an excess of
pyridine, whereas PdCl2 exhibits good activity in the absence of
Lewis acids, but requires an excess of base. Palladium(II) complexes
O
NO2
14
HN
+ ClCOOEt or (Boc)2O
28
OR'
Sn/NH4Cl
MeOH, ultrasound
R' = Et, tert.Butyl

Scheme 12.
79-93%
15
22
More recently, Tomkinson and co-workers have reported99 an

efcient protocol for the synthesis of N-aryl N-hydroxy carbamates
29, through a one-pot procedure involving zinc-mediated reduction
of nitroarenes 14 in the presence of chloroformates 7 (Scheme 13).
O
HO
NO2
+ ClCOOR2
14
OR2
Zn/NH4Cl
R2OH
5
29
Later, Shi and co-workers have reported108 a novel synthesis of

carbamates 6 through the oxidative carbonylation of amines 4 with

alcohols 5 using a PdCl2/ZrO2eSO2
4 catalyst system at 170 C
(Scheme 18).
R1NH2 + CO + R2OH
4
5
HOR2 + 1/2 O2
metal cat.
R2O
R1NHCOOR2
6
Shi and co-workers have reported109 an efcient and clean

synthesis of carbamates 6 through oxidative carbonylation of aromatic amines 4 using polymer-immobilised gold catalysts (Scheme
19).
Carbamates 6 have been prepared in good-to-excellent yields

through the reaction of amines 4, alcohols 5, carbon monoxide and
oxygen in the presence of novel metal catalysts. The metallic catalysts used during the oxidative carbonylations are palladium,100
platinum and alkali metal halides,101 or CO, Cu and Rh (Scheme
14).102 Pd and Cu halides have also been employed as catalysts
during the oxidative carbonylation process.103
CO +
O2
PdCl2-ZrO2-SO4
Scheme 18.
3.3. Oxidative carbonylation of amines
R1-NHCOOR2
6
Scheme 17.
Scheme 13.
R1NH2 +
O2
PVP-PdCl2-MXn
NaOMe, 89-97%
R1-NH2 + CO +
NHR1
R1NH2 + CO + R2OH
4
5
O2
Au/Polymer
R1NHCOOR2
6
Scheme 19.
Later, Shi and co-workers have also reported110 a highyielding efcient carbonylation of amines 4 with variety of alcohols 5 using a palladium complex-ionic liquid to afford carbamates 6. The desired products could be precipitated by adding
water into the resulting reaction mixture and the catalysts system could be reused with only a slight loss of catalytic activity
(Scheme 20).
Scheme 14.
The use of iodine promoted by a Pd catalyst,104 or a gold complex

with triphenylphosphine105 has also been reported in the synthesis
of carbamates (Scheme 15).
O2
R1NHCOOR2
R1NH2 + CO + R2OH
Pd(phen)Cl
2-[Bmim]BF4
5
6
4
Scheme 20.
O
R1NH2 +
CO +
HOR2 + I2
Pd cat.
R2O
NHR1
Scheme 15.
Mizuno and co-workers have reported106 the synthesis of 2oxazolidinone derivatives in which 2-aminoethanols 30 were easily subjected to thiocarboxylation with CO promoted by elemental
sulfur followed by oxidative cyclisation with molecular oxygen to
afford the corresponding 2-oxazolidinones 31 in good yields under
mild reaction conditions (Scheme 16).
Recently, Mei and co-workers have reported111 the synthesis of

methyl N-phenyl carbamates 6 through the oxidative carbonylation
of aniline 4, using a series of recoverable Co(salen) complexes in
zeolite-Y as catalysts, where the Co(salen) complexes were successfully encapsulated in zeolite-Y by a exible-ligand method
(Scheme 21). They studied the catalytic activity of various kinds of
Co(salen) complexes over zeolite-based catalysts.
O2
R1NH2 + CO + R2OH
Co(salen)in
zeolite
5
4
R1NHCOOR2
6
Scheme 21.
More recently, the synthesis of N-phenyl carbamates 6 through

the selenium-catalysed oxidative carbonylation of aniline 4 and
alcohols 5 in the presence of carbon monoxide and oxygen was
reported by Zhang and co-workers (Scheme 22).112
Scheme 16.
Wan and co-workers have reported107 an efcient synthesis of

carbamate esters 6, through the oxidative carbonylation of amines
4 with alcohols 5 using a PVP-polymer-supported palladium/
manganese bimetallic catalyst (Scheme 17).
3.4. Using metal/non-metal carbonates/bicarbonates

Carbonates and bicarbonates have been effectively employed for
providing a carbonyl functionality for the preparation of carbamates. A variety of metal carbonates, such as potassium carbonate
(K2CO3), sodium carbonate (Na2CO3), and caesium carbonate
23
Se
NH2 + ROH + CO + 1/2 O2
NH
OR
Et3N, 6 h, up to 85%
5
4
6
Scheme 22.
(Cs2CO3) have been used alone and in combination with different

catalytic systems. The synthesis of carbamates 6 through the reaction of variety of secondary amines 4 with structurally diverse
alkyl halides 32 was achieved using K2CO3/tetra-n-butylammonium hydrogen sulfate (Scheme 23).113 This method produces carbamates 6 as the major product along with a minor amount of Nalkylated amines 33.
Et4NHCO3
NH + R3.X
R2
32
O
NH + R3X
R2
32
(n-Bu)NHSO4
K2CO3
R1
N
R2
OR3
HN
Et4NHCO3
R2
OR3
( )n
35
N.R3
R2
34
R1
53-98%
Br-CH2(CH2)n-NH2.HBr
R1
R1
R1
n = 1, 56%
n = 2, 42%
Scheme 26.
33
Scheme 23.
Sodium carbonate has also been used in the synthesis of carbamates.114 Moreover, this method was not efcient for the production of only O-alkylated carbamates 6, due to the formation of
N-alkylated amines 33 (Scheme 24).
O
R1
NH + R3X
R2
Na2CO3
R1
N
R2
32
R1
OR3
NR3
+
R2
33
Scheme 24.
3.5. Synthesis of carbamates using carbon dioxide

Carbon dioxide has been frequently used, in various conditions
and forms, as a cheap and safe alternative for the synthesis of
carbamates,118 carbonates,119 and for several other interesting organic transformations.120 Carbamate synthesis using various forms
of carbon dioxide, such as gaseous, electrochemical, and supercritical has been achieved in recent years employing a diversity of
reagents and catalytic systems.
3.5.1. Gaseous carbon dioxide. Carbon dioxide 36 has a low reactivity,121 e.g., with amines 4 it forms unstable carbamic acids
37, which revert to their corresponding starting materials
(Scheme 27).
The role of Cs2CO3 in minimising the synthesis of N-alkylated

tertiary amines 33 during the one-pot, efcient synthesis of carbamates 6 from the corresponding alkyl halides 32 and amines 4
was rst investigated by Butcher115 (Scheme 25). He found that
Cs2CO3 was much better than K2CO3 in providing better yields of
carbamates from the corresponding alkyl halides and amines.
O
R1
NH + R3X
R2
Cs2CO3
R1
N
R2
32
R1
OR3
6
44-96%
NR3
+
R2
33
R-NH-COOH
R-NH2 + CO2
36
4
37
Scheme 27.
Yoshida and co-workers have reported122 the synthesis of carbamates 6, starting from CO2 36, amines 4 and unsaturated ethers
38 (Scheme 28). This method limits the carbamate synthesis to
those produced from secondary aliphatic amines. Moreover, it required longer reaction times (w70e80 h) and afforded low yields
(3e12%).
0-19%
Scheme 25.
O
R2NH + CO2 + CH2=CH-O-Et
Several bicarbonates have been used for the synthesis of carbamates. Of these, sodium bicarbonate (NaHCO3) has found use
in peptide chemistry.116 Inesi and co-workers have reported117
the synthesis of linear carbamates 6, starting from the corresponding primary and secondary amines 4 and alkyl halides 32
using tetra-ethylammonium hydrogen carbonate (Et4NHCO3) as
the carbonyl source (Scheme 26). The yields of carbamates were
affected by the nature of the alkyl halides used. They have
further extended the methodology to the synthesis of cyclic
carbamates 35 starting from the corresponding haloamines 34
using Et4NHCO3.
36
38
~70-80 h
3-12%
R2N
OEt
6
Scheme 28.
Later, Yoshida and co-workers have also reported123 the

synthesis of carbamates 6 through a one-pot reaction of amines
4 with alkyl halides 32 using gaseous CO2 (Scheme 29). The
carbamates obtained in this method are also limited to those
produced from primary and secondary aliphatic amines, and
require longer reaction times (w45 h), and afford low (6e25%)
yields.
24
O
R1
~ 45 h
NH + R3 X + CO2
R2
32
R1
6-25%
R2
36
OR3
Scheme 29.
Later, Ishii and co-workers have reported124 the synthesis of

carbamates 6 through a one-pot reaction of primary or secondary
aliphatic amines 4 with ortho esters 39using gaseous CO2 (Scheme
30). This method requires long reaction times and afforded carbamates in low yields.
Similarly, chloromethyl oxirane 44 or phenyl oxirane 48 on reaction with CO2 and aliphatic amines in methanol gave various
kinds of substituted carbamates127 46, 47, 50, 51 in 2e17% yields
through the involvement of intermediates 45, and 49, respectively
(Scheme 33).
Later, better yields have been reported by Yoshida and coworkers through the reaction of various epoxides 52 with a variety
of amines 4 using gaseous CO2 36 (Scheme 34).128 However, this
method leads to isomeric mixtures.
O
R1
+ CO2 +
2
52
R1
R'
NH
R''
36
HO
O
R2
R1
R'
R'
HO
R''
N
R''
R2
54
53
Scheme 34.
Kojima and co-workers have reported129 a carbamate synthesis

53 from epoxides 52, amines 4 and CO2 36, where the latter was
previously xed on an aluminium porphyrin (Scheme 35).
O
R1
R1
NH + CO2 + R3C(OR4)3
R2
R2
39
36
OR3
Scheme 30.
R1
Mono-carbamates of 1,2-diols 41 have been synthesised125 from

the corresponding 1,2-epoxides 40 through the reaction of primary
and secondary aliphatic amines using gaseous CO2 (Scheme 31).
About half of the epoxide is lost, however, due to the accompanying
nucleophilic ring opening by the amine to afford the N-alkylated
products 42.
R1
NH
R2
+ CO2 +
36
OH
22-24 h
R1
42-52%
40
O C
41
OH
R1
+
N
R2
R1
52
+ CO2 +
36
R'
R''
aluminium porphyrin
NH
HO
O
R2
R'
N
53
R''
Scheme 35.
Toda have reported130 the synthesis of cyclic carbamates

through the reaction of carbon dioxide with a-bromoacylophenones 55 in the presence of aliphatic primary amines in methanol
to afford 3-alkyl-4-hydroxy-oxazolidone-2 derivatives 57 under
mild reaction conditions (Scheme 36).
R2
42
Scheme 31.
The mono-carbamates 41 could also be obtained,126 starting

from epoxide 40, using tetrakis(dimethylamino)titanium(IV) 43
and gaseous CO2 (Scheme 32), but this method was not satisfactory,
due to its longer reaction time (w3e4 days), and it afforded low
yields (5e20%).
Ti(NMe2)4 + CO2 +
43
R1
5-20%
40
Scheme 36.
OH
~ 3-4 days
O C
41
N
R2
R1 & R2 = Me
Scheme 32.
This reaction led to the formation of bis(2-oxazolidinones)131 60

when 2-methoxy 3,3-dimethyl-2-phenyloxirane 56 or a-bromoiso-butyrophenone 55 was reacted with CO2 and aliphatic a,u-diamines 58 (Scheme 37).
Scheme 33.
25
However, this method was only useful for the preparation of

carbamates from primary and secondary aliphatic amines. The effect of several strong bases (CyTMG, TMG, DBU, MTDB, CyTEG, etc.)
in increasing the nucleophilicity of 45 resulted in the formation of
carbamates 6, studied by McGhee and co-workers134 They have
demonstrated the role of various strong bases in yielding O-alkylated carbamate products using various kinds of alkylating agents
(Scheme 42).
2 RNH2 + CO2
4
36
32
R' X
RNH-COONH3R
base, 40-78%
45
H
N
R'
O
6
Scheme 42.
Scheme 37.
The reaction of 2-(1-haloalkyl)-oxiranes 61 with carbon dioxide

and aliphatic primary amines gave ve and six-membered cyclic
carbamates 62, 63 (Scheme 38).3a
O
45
R'NH-COONH3R'
O
Br
O
R'
61
R'
O
OH
OH
63
62
Scheme 43.
Scheme 38.
In the above reaction, it was shown that there is an ionic species

45 involved, which is formed when 2 mol of amine 4 was reacted
with CO2 36 (Scheme 39).
R-(CH2)n-CH2.X +
Scheme 39.
70
An improvement in the yield of carbamate has been achieved by

using different basic reagents, which might be helpful in increasing
the nucleophilicity of the ionic species 45. Thus, Hori and coworkers have reported132 the synthesis of carbamates 6 through
the reaction of primary and secondary amines 4, CO2, and alkyl
halides 32 in the presence of a strong proton acceptor like DBU
(Scheme 40).
R1
R3X
32
CO2, DBU
NH
+
R2
R2
NH
DBU-CO2 complex
5 oC, 24 h, 80-98%
RNH-COONH3R
R2
R3P + CCl4
45
18-crown-6
72
73
[ R3P-CCl3] Cl
OH
R2
H
R3
PR3
O
33-93%
R2
R3
R
O
H
Scheme 45.
R'
N
6
Scheme 41.
R'
74
NHR'
CO2-Et3N
N
R'
R2
Cyclic carbamates137 75 could be obtained in good yields

(33e93%) under mild reaction conditions from amino alcohols
74 and carbon dioxide using phosphorus(III) reagents 72 [i.e.,
Ph3P, (PhO)3P] and halogenoalkanes (i.e., CCl4 and CCl3$CCl3) 73
(Scheme 45).
H
R3
R1
N
Scheme 44.
32
R' X
O
71
R2
Aresta and Quaranta have reported133 the synthesis of carbamates 6 employing ionic species 45 through the alkylation with
alkyl halides 32 using 18-crown-6 as a phase-transfer catalyst
(Scheme 41).
R-(CH2)n-CH2
R1
Scheme 40.
2 RNH2 + CO2
4
36
R1
N
R3
Later, Perez and co-workers have reported136 the synthesis of Nalkyl carbamates 71 in good-to-excellent yields through a clean and
mild transcarboxylation of several amines 4 with the previously
synthesised DBUeCO2 complex and subsequent O-alkylation by
different alkyl halides 70 (Scheme 44).
RNH-COONH3R
45
2 RNH2 + CO2
4
36
O-Allyl carbamates2c,135 69 could be obtained by the addition of

preformed carbamate ion 67 [R$R0 NHeCOO Hbase], generated
from various primary and secondary amines 4 and CO2, to a THF
solution of allylic chlorides 68 containing a palladium/phosphine
catalyst (Scheme 43).
75
26
Tominaga and Sasaki have reported138 an efcient protocol

for the synthesis of 2-oxazolidinones 75 from CO2 and 1,2-amino
alcohols 74 catalysed by n-Bu2SnO affording 53e94% yields
(Scheme 46).
The use of Amberlite IRA 400 resin (basic resin) in the synthesis
of carbamates 6 in high yields through the reaction of a variety of
alcoholic tosylates 78 with various amines 4 was also reported by
our group (Scheme 51).143
R1
R2
R3
+
HN
R2
n-Bu2SnO
CO2
R2
RHN
69-99%
OH
N
O
R3
R1
X + HN
R2
R3
R1
dry DMSO, basic resin/CO2
R2
100oC, 2-4 h, 70-98%
R,
R3
79
R
N
R,
Scheme 52.
A direct synthesis in high yields of carbamates 6 from the primary alcohols 5 and amines 4 using a Mitsunobu reagent/CO2
system has been rst reported by our group (Scheme 53).145
R2
77
R. (CH2)n. CH2.OH +
Scheme 47.
More recently, they have further extended their protocol for the
synthesis of carbamates 6 through the reaction of secondary
amines 4 with primary and secondary alcohols 5 using gaseous CO2
through a Mitsunobu reaction employing DBU and a DBAD/Bu3P
system (Scheme 48).140
NH
4
R1
CO2 , Ph3P/DEAD
2-4 h, 80-98%
R. (CH2)n. CH2.O
R2
Scheme 53.
Recently, the above method for the preparation of carbamates 6

was further extended to a variety of primary, secondary and tertiary
alcohols 5 and amines 4, using the Mitsunobu reagent/CO2 system,
by our group (Scheme 54).146
R1
NH
R2
R,
R3
76
The utility of basic resin in the synthesis of carbamates 6 in high

yields from the corresponding alkyl halides 32 and amines 4 using
gaseous CO2 was investigated by our group (Scheme 52).144
R
Mitsunobu reaction
R3
75
The synthesis of cyclic carbamates 77 from amino alcohols 76

involving sequential carboxylation with carbon dioxide followed by
a Mitsunobu reaction was reported by Dinsmore and Mercer.139
Unexpectedly, the stereochemical course of the Mitsunobu reaction is dependent on whether the carbamic acid intermediate is
N-substituted with hydrogen (retention) or carbon (invertion)
(Scheme 47).
CO2
Scheme 51.
Scheme 46.
R2
100oC, 2.5-4 h, 70-98%
R,
78
74
R1
dry DMSO, basic resin/CO2
R3
R'
O.Tos + HN
R1
R3
180oC, 16 h, 53-94%
OH
'
+ CO2 + HO
R3
DBU, DBAD/Bu3P
R4
100oC, 45 min., 46-96%
R1
R3
R1
R2
R4
R3
5
We have reported141 an efcient, one-pot, high-yielding protocol

for the synthesis of carbamates 6 through the reaction of various
amines 4 with variety of alkyl halides 32 using a benzyltrimethylammonium hydroxide (Triton-B)/CO2 system (Scheme 49).
O
32
R1
NH
R2
Triton-B, CO2, 90-100oC

3-5 h, 80-98%
R-(CH2)n-CH2.
OH + HN
R2
Scheme 48.
R-(CH2)n-CH2.X +
R4
R1
N
90-100oC, 2-5 h, 76-98%
R5
We have also reported142 the synthesis of carbamates 6 in high

yields through the reaction of a variety of alcoholic tosylates 78
with various amines 4 using the Triton-B/CO2 system (Scheme 50).
R2
NH + CO2 + RCH2CH2CH2Br
R2
O.Tos + HN
R3
R,
dry DMSO, Triton-B, CO2

60oC, 2-4 h, 76-98%
R3
78
Scheme 50.
O
O
R2
R5
32
zeolite-Y
cat.
R1
NCOOCH2CH2CH2R
R2
Scheme 55.
Srivastava and co-workers have also reported148 an efcient

protocol for the synthesis of carbamates 6 using CO2 mediated by
zeolite-based organiceinorganic hybrid catalysts (Scheme 56).
R
N
R,
The use of zeolite-based catalysts in the synthesis of carbamates

6 was investigated by Srivastava and co-workers through the reaction of the corresponding amines 4, gaseous CO2 and alkyl halides
32 over either titano-silicate molecular sieves or metal pthalocyanine complexes encapsulated in zeolite-Y. The catalysts could be
used with little or no loss in activity (Scheme 55).147
R1
R1
R3
R2
R2
R4
Scheme 54.
Scheme 49.
R1
R1
dry DMSO, Mitsunobu reagent/CO2
R1
NH + CO2 + RCH2CH2CH2Br
R2
32
zeolite-based
cat.
Scheme 56.
R1
NCOOCH2CH2CH2R
R2
Recently, Singh has reported the synthesis of various kinds of

methyl carbamates 6 through the corresponding amines 4 and
methyl iodide 32 using a tetra-ethylammonium bromide-superoxide/CO2 system (Scheme 57).149
R1
KO2/Et4NBr/CO2
+ MeI
HN
R2
DMF, rt, 2-7 h
32
R1
N
R2
Sasaki and Dixneuf have also reported154 the synthesis of 2oxoalkyl substituted carbamates 85 in good yields through the reaction of secondary amines 4, a-ethynyl alcohols 84 and CO2 using
Ru3(CO)12 as the catalyst (Scheme 62).
R3
OMe
R4
OH
HN
R2
+ MeI
32
77.5-95.5%
80oC, 20 h, 4-64%
R2
R1
N
R2
OMe
Matsudo and co-workers have reported155 a synthesis of enol

carbamates 83 in good yields with high regio and stereoselectivity
through the reaction of amines 4, terminal alkynes 79 and gaseous
CO2 in the presence of a catalytic amount of (h4-cyclo[Ru(COD)(COT)]
octadiene)(h6-1,3,5-cyclooctatriene)ruthenium
and a tertiary phosphine (Scheme 63). They have further extended
their methodology to the synthesis of cyclic enol carbamates 87
using N-substituted propargyl amines 86 and CO2.
O
+ CO2
R2NH + R
4
79
36
200oC, 24 h,
83
100oC, 8-48 h
63-80%
87
NHR1
24-90%
[Ru]/PR'3
86
R2O
C
N
100oC, 8-48 h
37-62%
tin complexes
R1
[Ru]/PR'3
R2
CH2NHR + CO2
HOR2
R4
Carbon dioxide has been converted into carbamates 6 through

the reaction of various amines 4 with a variety of alcohols 5 catalysed by tin complexes.151 The addition of acetals as dehydrating
agents under a high CO2 pressure is the key to achieving high yields
(Scheme 59).
CO2 +
85
Scheme 58.
R1NH2 +
R3
N
Scheme 62.
DMF, MW, 5-7 min.
R1
84
Singh and co-workers have further investigated150 an improved

and efcient protocol for the synthesis of methyl carbamates 6,
through the reaction of the corresponding amines 4 with methyl
iodide 32 using the tetra-ethylammonium bromide-superoxide/
CO2 system under microwave conditions (Scheme 58).
KO2/Et4NBr/CO2
Ru3(CO)12
R2
Scheme 57.
R1
R1
NH + CO2 +
38-90%
27
Scheme 63.
Scheme 59.
Sasaki and Dixneuf have rst reported152 the synthesis of vinyl

carbamates (80, 81 and 82), starting from diethylamine 4, and alkynes 79 using CO2 in the presence of a ruthenium catalyst
Ru3(CO)12 (Scheme 60). The overall yields of the products are poor
in most of the reactions.
Later, Dixneuf and co-workers have reported156 the synthesis of

vinyl carbamates 83 through the reaction of an alkyne 79 with an
amine 4 using gaseous CO2 in the presence of various kinds of ruthenium complexes, i.e., RuCl2(PR3)(carene) and RuCl2(nor-bornadiene)(pyridine)2 (Scheme 64). They have studied the catalytic role
of different Ru complexes in affording better yields of vinyl
carbamates.
O
R1
+ CO2
+ R
HN
C
N
3-67%
79
R2
R1
Ru complex
R2
83
Scheme 64.
Later, Sasaki and Dixneuf have reported153 a direct synthesis of

vinyl carbamates 83 in good yields through direct the reaction of
secondary amines 4 with acetylene 79 using gaseous CO2 in the
presence of a catalytic amount of RuCl3$3H2O (Scheme 61).
O
R2NH + R
4
+ CO2
79
RuCl3.3H2O
R1
R2
83
Scheme 61.
R1
C
N
90oC, 10-46%
Scheme 60.
Shim and co-workers have synthesised157 carbamates 89

through the reaction of amines 88, acetylenic alcohols 84 and carbon dioxide using a lanthanide catalyst. Thus, the reaction of perhydroazepine
88
with
3,3-dimethyl-prop-1-yne-3-ol
84
(R1R2Me) and CO2 in the presence of MCl3 (MCe, Pr, Nd, Gd)
gave carbamate 89 (n6) in 20e38% yields. They have also prepared the carbamates (n4, 5) in 31 and 21% yields (Scheme 65).
NH +
(CH2)n
88
HO
R2
+ CO2
MCl3
20-38%
(CH2)n
R1
O
R2
89
84
R1 = R2 = Me
Scheme 65.
28
Dixneuf and co-workers have reported158 a regioselective synthesis of O-1-(1,3-dienyl)carbamates 91 through the regioselective
addition of CO2 and secondary amines 4 to isopropenylacetylene 90
in the presence of [Ph2P(CH2)nPPh2]Ru(h3-CH2eC(Me)]CH2)2 as
the catalyst (Scheme 66). The yields were dependent on the nature
of the ligand used in the catalyst. These workers found ligand with
n2, afforded better yields of the products. The addition is favoured
in the case of secondary cyclic amines.
Merrield resin 94 and caesium carbonate/CO2 and TBAI as

a phase-transfer catalyst (Scheme 70).
O
Cl +
R1
NH
R2
94
R1
N
CO2, Cs2CO3, TBAI
R2
DMF, 60oC, ~24 h 55-97%
95
Scheme 70.
90
R2NH +
4
[ R2NCOO H2NR2]
CO2
36
100oC,
R2N
Ru cat., 20 h
45
O
O
91
up to 80%
Scheme 66.
Kim and co-workers have reported159 the synthesis of carbamates 93 through the reaction of various kinds of propargyl alcohols 92 with variety of amines 4 using gaseous CO2 in the presence
of a catalytic amount of {Cu (X) (BF4)2 (X2, 5, 19, 22, tetraaza
[6,6](1,10 )-ferrocenophane-1,5-diene)} (Scheme 67).
Later, these workers have reported the synthesis of carbamates162 6 in the solution phase through the reaction of various
kinds of structurally diverse aliphatic, aromatic and heterocyclic
amines 4 with a variety of alkyl halides 32 using the caesium carbonate/CO2 system in the presence of a catalytic amount of TBAI
(Scheme 71).
RCH2X +
R4
R2
OH +
R1
NH
R5
R3
[M]/bipy, CO2
100 C, 24 h, 30-97%
R3
DMF, 23oC, 47-96%
RH2C
R2
Scheme 71.
R1
CO2, Cs2CO3, TBAI
R4
O R
2
R1
NH
R2
32
R1
R5
92
93
They extended their methodology to the synthesis of peptidomimetics 97 and 99 using various kinds of protected amino acids 96
and 98 (Scheme 72).
Scheme 67.
Recently, Bhanage and co-workers have reported160 the synthesis

of vinyl carbamates 83 through the reaction of various kinds of alkynes
79, amines 4, and CO2 using ruthenium tris(2,2,6,6-tetramethyl-3,5heptanedionate) [Ru(TMHD)3] as a catalyst (Scheme 68).
Ph
H2N
TBAI, DMF, 23oC, 12 h
COOPh
96
PhH2CO
R1
+ CO2 + HN
79
R2
[Ru(TMHD)3]
100oC, 24 h, up to 55%
R1
Carbon dioxide providing the carbonyl functionality for the

synthesis of carbamates is not sufcient in itself in yielding high
yields of desired carbamates. Therefore, several researchers have
considered that adding basic reagents to the reaction mixture may
increase the basicity and nucleophilicity of the ionic species 45.
Consequently, it has been proposed that metal carbonates, such as
Na2CO3, K2CO3, Cs2CO3 etc. are good basic reagents, which could
provide a carbonyl functionality in addition to its basic properties.
Based on this concept, there are many reports that have appeared in
the recent past on the use of metal carbonate/CO2 systems for the
synthesis of carbamates. Thus, Butcher has reported115 a carbamate
synthesis 6 in good-to-excellent yields (58e96%) from various alkyl
halides 32 and amines 4 using the caesium carbonate/CO2 system
(Scheme 69).
O
RCH2X +
32
R1
NH
R2
R2
6
Scheme 69.
Later, Jung and co-workers have reported161 the synthesis of

carbamates 95 in good-to-excellent yields using a solid-phase
COOMe
A direct synthesis of N-alkyl carbamates 6 from primary amines

4 and alkyl halides 32 using the caesium carbonate/CO2 system has
been reported by Jung and co-workers (Scheme 73).163
O
RNH2 +
4
R'X
32
CO2/Cs2CO3,TBAI,
DMF, 23oC, 20 h-6 d
52-92%
N
R'
R'
O
6
Scheme 73.
A study of the comparative yields of carbamates 6 using different metal carbonates and bases on O as well as N-alkylated products was reported by Shi and Shen (Scheme 74).164 They realised
that the best yields (>87%) of carbamates could be achieved using
a DBU/CO2 system.
N
RH2C
NH
99
R1
CO2, Cs2CO3
DMF, 58-96%
PhH2CO
Scheme 72.
83
Scheme 68.
COOPh
92%
98
R2
R
COOMe
ClH2N
TBAI, DMF, 23oC, 24 h
NH
97
87%
BzCl, CO2, Cs2CO3
Ph
BzCl, CO2, Cs2CO3
BnX +
32
BnNH2
CO2, base, solvent

metal carbonate
Bn
NHBn
6
Scheme 74.
We have reported165 a convenient, high-yielding, one-pot synthesis of carbamate esters (70e90%) from the corresponding
alcoholic tosylates 100, and amines 4 using the K2CO3/CO2 system

in the presence of a catalytic amount of tetra-n-butylammonium
iodide (Scheme 75). This method has been used for carbamates
derived from various aliphatic primary, secondary and aromatic
amines.
R1
RCH2OTos +
NH
R2
100
R1
dry DMSO, anhyd. K2CO3

TBAI, CO2, 90-100oC, 5-6 h, 70-90%
RCH2 O
Later, Inesi and co-workers have reported170 the synthesis of

carbamates 6 using carbon dioxide through an electrochemical
process (Scheme 80). This synthesis is based on the reaction of
amines 4 with the electrochemically generated base 102 (associated with the Et4N cation) from 2-pyrrolidone 101 followed by
sequential addition of CO2 and ethyl iodide, affording the carbamates in high yields.
e , MeCN, Et4NClO4
R2
Scheme 75.
Vos and co-workers have reported166 an efcient and green

synthesis of carbamates 6 through the coupling of various amines 4
with variety of alcohols 5 using the Cs2CO3/CO2 system (Scheme 76).
O
R1
NH + CO2 + ROH
R2
OR
up to 69%
R1
Cs2CO3
R2
29
Scheme 76.
Recently, a synthesis of radiolabelled carbamates 6 through the

incorporation of [11C]eCO2 using various kinds of alkyl halides 32,
amines 4 and catalytic amount of DBU was reported by Hooker and
co-workers (Scheme 77).167
2. CO2
O
N
3. EtI
NEt4
33-89%
102
N
H
101
R1
NH + RCH2Cl
R2
32
11
CO2
R1
75oC, 10 min,
77%
R2
DBU,
Inesi and co-workers have also reported171 an improved electrochemical synthesis of chiral oxazolidin-2-ones 75, starting from
the corresponding chiral 1,2-amino-alcohols 74. Subsequent CO2
bubbling and addition of tosyl chloride afforded the desired cyclic
carbamates 75 in high yields (Scheme 81).
OH
H2N
MeCN-Et4NClO4
R2
R1
11
74
R2
CO2
DBU, DMS in DMF

1 min, up to 96%
R1
R2
75
O
R2
O
11
66-88%
The utility of an electrochemically generated cyanomethyl anion/carbon dioxide system in affording high yields of carbamates 6
using various kinds of amines 4 and alkyl halides 32 was further
investigated by Inesi and co-workers (Scheme 82).172
R1
Scheme 81.
A synthesis of labelled carbamates 6 has been reported by

Wilson and co-workers through the trapping of labelled CO2
with amines 4 using a methylating agent, i.e., dimethylsulphate
(Scheme 78).168
NH
HN
Scheme 77.
R1
2. CO2
3. TsCl
OR
R2N-COOEt
6
Scheme 80.
1. e
O
1. R2NH
R1
N
R2
NH
Scheme 78.
3.5.2. Electrochemical carbon dioxide. Inesi and co-workers have

rst reported169 the synthesis of linear carbamates 6 and cyclic
carbamates 35 from the corresponding amines 4, alkyl halides 32 or
haloalkylamines 34 using electrogenerated-superoxide activated
carbon dioxide (O2/CO2) (Scheme 79).
CH2CN/CO2
EtI
R1
R2
up to 96%
OEt
Scheme 82.
Inesi and co-workers have reported173 a new electrochemical

procedure for the synthesis of carbamates 6 in high yields, starting
from the corresponding amines 4, and alkyl halides using electrochemical carbon dioxide-saturated room temperature ionic liquid
[Bmim]BF4 solutions (Scheme 83).
O
R1
NH + CO2
R2
[Bmim]BF4, e
EtI, up to 82%
R1
N
R2
OEt
Scheme 83.
Scheme 79.
Dunach and Tascedda have reported174 a new and selective

electrochemical procedure for the synthesis of ve-membered-ring
cyclic carbamates 104 and 105 involving nickel-catalysed CO2 incorporation into aziridines 103 under mild electrochemical conditions (Scheme 84). Out of several Ni catalysts used, Ni(bipy)3(BF4)2
was shown to be efcient for this transformation and afforded 100%
yields of the desired carbamates.
30
R'
Ni(II) +
+ CO2
R'
R'
DMF, rt
(1 atm.)
75-100%
103
O + O
N
R
104
105
Scheme 84.
Lu and co-workers have reported175 a new and efcient electrochemical synthesis of carbamates 6 through the electrochemical
incorporation of carbon dioxide into amines 4 catalysed by an
electrogenerated Ni complex [Ni(bipy)3Cl2] using tetra-ethylammonium bromide (Scheme 85).
Recently, Jiang and co-workers have demonstrated178 a new and

efcient protocol for the synthesis of oxazolidinones 106 and
oxazolones 107 through the cycloaddition reaction of CO2 with
propargyl alcohols 84 and amines 4 under supercritical conditions
(Scheme 88).
Ikariya and co-workers have reported179 the stereoselective
synthesis of Z-alkenyl carbamates 83 from the corresponding
amines 4 and alkynes 79 using a CO2-soluble ruthenium-P(OEt)3
catalyst under supercritical conditions (Scheme 89).
R1
R
RuCl2{P(OEt)3}4
+ HN
79
NH + CO2
R2
EtI, up to 82%
OEt
R2
Scheme 85.
3.5.3. Supercritical carbon dioxide. Yoshida and co-workers have

rst reported176 the synthesis of carbamates 6 in good yields,
starting from the corresponding amines 4 and alkyl halides 32
using supercritical CO2/K2CO3 in the presence of tetra-n-alkylammonium halides acting as phase-transfer catalysts (Scheme 86).
They have also demonstrated the role of different phase-transfer
catalysts on carbamate synthesis and found that tetra-n-butylammonium bromide was the best in affording high yields of
carbamates.
O
R1
R2
NH + R3X + K2CO3
onium salt, CO2
1- 4 h,72-94%
32
R1
R3
R2
6
Scheme 86.
Baker and co-workers have reported177 a solvent-free ruthenium-catalysed synthesis of vinyl carbamates 83 through the reaction of phenylacetylene 79 with diethylamine 4 using
supericritical CO2 (Scheme 87). They have also studied the effect of
temperature on the catalytic activity of Ru complexes and found
that the best yields of vinyl carbamates were obtained at 120 C.
O
R1
+ CO2 + HN
Ph
79
RuCl3.xH2O
R2
R1
N
R2
3 h, 60-120oC
Ph
100%
83 (E and Z)
Scheme 87.
R1, R2 = alkyl, aryl

32-95%
R1
OH +
R2
84
R3
NH2
R3
R3
R1
R2
scCO2, CuI
106
60oC, 12-24 h
R1 = alkyl, aryl, H
R2 = H
88-96%
O
R1
Scheme 88.
107
R1
N
R2
31-68%
83 (Z)
Scheme 89.
R1
Ni(bipy)3Cl2
scCO2, 15 h, 80oC
R2
O
R1
Ikariya and co-workers have also reported180 the synthesis of 5vinyl-1,3-oxazolidin-2-ones 109 through the carboxylative transformation of 2,3-allenic amines 108 and CO2 promoted by palladium catalysts under supercritical conditions (Scheme 90).
R1
Pd(OAc)2
NH
R2
R1
scCO2, 50oC, 15 h
up to 65%
108
R2
109
Scheme 90.
3.5.4. Organic carbonates with carbon dioxide. Organic carbonates

constitute an important source for the carbonyl functionality
during the synthesis of carbamates. Their reaction with amines
represents an alternative synthetic route to carbamates that has
gained growing attention in the last few years as a nonphosgene route to the synthesis of organic carbamates.181
Nowadays, dimethyl carbonate (DMC) 110 can be produced on
a large scale by the oxidative carbonylation of methanol.182
Other organic carbonates can be easily obtained by transesterication of DMC with phenols183 and long-chain highboiling alcohols.184 The reaction between primary and secondary
amines and dialkyl carbonates needs a suitable catalyst in order
to obtain satisfactory conversion rates and high selectivities.
Strong bases, such as alkali metal alkoxides as well as Zn, Co, Sn
and Al compounds, have been widely employed as catalysts in
the carboalkoxylation of anilines and, more generally, of aromatic amines.185 Moreover, Lewis acids, such as AlCl3, SnCl2,
ZnCl2, Zn(OAc)2$2H2O, FeCl3, or metal (Rh,Ru) complexes, have
proved to be effective in promoting the conversion of n-propylamine and diethyl carbonate selectively into n-propylethyl
carbamate.182
Primary and secondary aliphatic amines can react with CO2
according to the equilibrium shown in Eq. 1 to afford the
monoalkylammonium-alkylcarbamate (MAAAC) ion121 45 that
serves as a convenient source of the carbamate moiety in the
synthesis of carbamates using DMC (Scheme 91).186 O-Carbomethoxylation of the carbamate anion is the rst step (Eq. 2) to
afford a mixed carbamicecarbonic anhydride RNHeCOOCOMe
111. This step could be catalysed by acidic species, such as RNH
3
or RNHeCOOH, present in the equilibrium. Selective decarboxylation of 111 through the expulsion of a CO2 molecule
from the carbamic moiety leads to the formation of carbamate 6
(Eq. 3).
2RNH2 + CO2
4
OMe
45 + O
+ MeOH
O
OMe
The use of N,N0 -disuccinimidyl carbonate 114 has been further

explored for the synthesis of carbamates189 118 from azides 117 and
mixed carbonates 116 obtained from 115 by Ghosh and co-workers
(Scheme 94).
Ghosh and co-workers have also reported190 the synthesis of
carbamates 122 in high yields, starting from the corresponding
amines 121 and a mixed carbonate 120, which is obtained through
a reaction of alcohol 119 with DSC 114(Scheme 95).
Chiral carbamates 125 have also been synthesised through an
enzymatic alkoxy-carbocyclisation reaction with vinyl carbonates
123 and racemic amines 124 using Candida antarctica lipase (CAL),
was reported by Pozo and Gotor (Scheme 96).191
Gotor and co-workers have reported192 the chemoenzymatic
synthesis of a 20 -deoxynucleoside urethane. 20 -Deoxynucleoside50 -and 30 -(N-alkyl)carbamates (129 and 131) were synthesised in
a two-step procedure using lipase catalysis in the regioselective
vinyloxy carbonylation, starting from 96 and 97 through the
involvement of intermediates 128 and 130 (Scheme 97). The
regioselectivity of the reaction depends upon the type of
lipase enzyme used. Total regioselectivity is obtained in the
presence of PS lipase and only a small amount of the regiose-
(eq. 1)
RNH-COONH3R
45 OMe
(eq. 2)
NHR
111
110
OMe
111
+
NH2R
C
6
31
CO2 (eq. 3)
Scheme 91.
Organic carbonates have received much attention in recent

years as cheap and safe alternatives to the non-phosgene routes for
the synthesis of organic carbamates. Therefore, several researchers
in different countries have become interested in synthesising carbamates through this route.
Ogura and co-workers have rst reported187 an efcient synthesis of N-succinimidyl carbamates 113 through the reaction of the
corresponding amines 4 with N,N0 -disuccinimidyl carbonate (DSC)
112 using triethylamine (Scheme 92).
O
O
N
R1
N
112
Et3N, rt
+ HN
O
R1
N
N
5-10 h, 50-90%
R2
R2
113
Scheme 92.
Later, Ogura and co-workers have demonstrated188 an efcient

protocol for the synthesis of carbamates 6 through the reaction of
the corresponding amines 4 with benzotriazole carbonates 114
(Scheme 93).
N
N
R1
+ HN
N
O
OR
53-98%
R2
R1
rt, 0oC
R2
lective product is obtained when the reaction is catalysed by CA

lipase.
Aresta and co-workers have reported193 the synthesis of carbamates 6 through the reaction of aromatic amines 4 with DMC
110 or diphenyl carbonate (DPC) 132 in the presence of organophosphorous acids [Ph2P(O)OH, (PhO)2P(O)OH, or (BuO)2P(O)OH/
(BuO)P(O)(OH)2 equimolar mixtures] (Scheme 98). They have
further realised that better yields of carbamates were obtained
using DPC.
OR
114
Urpi and co-workers have reported62d an efcient protocol for

the synthesis of tert-butyl carbamates 6 through the reaction of
Scheme 93.
O
O
O
O
114
OH
Et3N, MeCN, 23oC
+ N3
N
O
115
116
69-80%
117
Et3N, THF H2, 10% Pd/C
O
O
O
O
N
H
118
Scheme 94.
O
O
32
OTBS
TBSO
114
HO
Et3N, MeCN, rt, 4 h
119
O
O
120
O
O
O
H
Et3N, CH2Cl2
121
rt, 3 h
65-89%
NH2
Ph
OTBS
O
H
Ph
N
H
O
122
Scheme 95.
O
C
RO
O
CAL
+
O
123
H2N
124
P-acid
ArNH2 +
20-72 h, 38-45% RO
up to 98% ee
N
H
RO
OR
15-76 h, up to 98%
Scheme 96.
Scheme 98.
azides with trimethylphosphine 133 followed by the addition of 2(tert-butoxycarbonyloxyamino)-2-phenyl acetonitrile 134 to 135 at
20 C (Scheme 99).
Chandrasekhar and co-workers have reported194 an excellent
one-pot method for the synthesis of carbamates 6 through the
reaction of azides or Cbz-protected amines with di-tert-butyl
dicarbonate (Boc)2O 136 using an inexpensive and safe hydride
source, i.e., polymethylhydrosiloxane (PMHS) under PdeC catalysis
(Scheme 100).
The lipase enzyme has also been used as a catalyst in the synthesis of chiral carbamates195 138, starting from racemic amines 4
and alkylvinyl carbonates 137 (Scheme 101).
Leunaire and co-workers have reported196 an efcient synthesis
of carbamates 6 through the reaction of amines 4 with DMC 110
catalysed by g-Al2O3 (Scheme 102).
RN3
133
Me3P
O
O
Ph
N
CN
C
O
135
134
30oC, 128a
5oC, 128b
HO
RHN
HO
80-100%
128
RNH2, THF, 80-100oC
RNH2, THF, 80-100oC
PSL, THF, 30oC
130
Scheme 97.
HO
O
O
RHN
131a, 80%
131 131b, 52%
OBut
N
H
CAL, THF
127
5 h, 87-100%
Scheme 99.
126
HO
-20oC, rt
+ RN=PMe3
OBut
O
O
HO
OR
110, R = Me
132, R = Ph
125
HO
ArHN
129
129a, 70%
129b, 75%
33
Selva and workers have reported199 an efcient synthesis of carbamates 6 from primary aliphatic amines 4 with dialkyl carbonates
(R1Me, 110; R1Ph, 139) in supercritical CO2 (Scheme 105).
Scheme 105.
Scheme 100.
Sodeoka and co-workers have reported200 a convenient method

amines 4 with a variety of polymer-supported N-hydroxy
succinimide-substituted carbonates 140 (Scheme 106).
Later, Christensen and co-workers have reported201 the synthesis of carbamate-protected polyamines (145e147, 149, 150 and
151) from 144 and 148 using alkyl phenyl carbonates (141e143).
This is an economical, practical and versatile method for the selective Boc, Cbz and Alloc protection of polyamines. This method
allows Boc, Cbz and Alloc protection of primary amines in the
presence of secondary amines by reaction of polyamines with alkyl
phenyl carbonates. In addition, this method allows the monocarbamation of simple symmetrical aliphatic a,u-alkanediamines
in high yields with respect to the diamine. Furthermore, the
method allows the selective carbamate protection of a primary
amine located on a primary carbon in the presence of a primary
amine located on a secondary or a tertiary carbon in excellent yields
(Scheme 107). The alkyl phenyl carbonates investigated in this
Scheme 101.
Scheme 102.
Scheme 106.
Chaudhari and co-workers have reported197 efcient protocol

carbonates (R2Me, 110; R2Ph, 132) with a variety of amines 4
catalysed by silica-gel (Scheme 103).
Scheme 103.
Carloni and co-workers have reported198 synthesis of carbamates 6 through the reaction of diethyl carbonate 139 with a variety of amines 4 using a heterogeneous catalyst-a hybrid organic/
inorganic material prepared by anchoring TBD to MCM-41 silica
(Scheme 104).
Scheme 107.
Scheme 104.
study were tert-butyl phenyl carbonate (141), benzyl phenyl carbonate (142) and allyl phenyl carbonate (143), which introduces the
Boc, Cbz and Alloc protecting groups.
Curini and workers have reported202 that ytterbium triate,
Yb(OTf)3, can be efciently used for the preparation of carbamates
34
6, through the reaction of various amines 4 with DMC 110 under

solvent-free conditions (Scheme 108).
presence of potassium carbonate and tetra-n-butylammonium

bromide under solvent-free conditions (Scheme 113).
Scheme 113.
Scheme 108.
Deng and co-workers have reported203 the synthesis of carbamates 6 through the reaction of primary and secondary aliphatic
amines 4 with DMC 110 using ionic liquids (Scheme 109).
Distaso and Quaranta have reported208 a high-yielding synthesis

of carbamates 6 through the reaction of various aliphatic amines 4
and dimethyl carbonate (110) catalysed by group III metal (Sc, La)
triates, under mild reaction conditions (Scheme 114). Sc(OTf)3 is
more effective than the La salt.
Scheme 114.
Scheme 109.
Conversion of azides into tert-butyl carbamates204 6 could also

be achieved using di-tert-butyl dicarbonate 136, decaborane
(20 mol %) and 20% PdeC at room temperature in methanol
(Scheme 110).
Distaso and Quaranta have also reported209 the carbomethylating reactivity of methyl phenyl carbonate 153 towards aromatic
amines 4 in the presence of a group III metal (Sc, La) triate catalyst
under mild conditions to afford the corresponding carbamates 6 in
high yields (Scheme 115). They have optimised the effect of the
various catalysts at different temperatures, times and molar ratios
of amines on the yields of the carbamates. Sc(OTf)3 is more effective
than the La salt.
Scheme 110.
Chandrasekhar and co-workers have reported205 the one-step

conversion of N-benzyl, N-trityl and N-diphenyl amines 152 into
tert-butyl carbamates 6 using (Boc)2O 136 the presence of polymethylhydrosiloxane (Scheme 111).
Scheme 115.
Simon and co-workers have reported210 an efcient synthesis of

o-nitrophenyl carbamates 6 through the reaction of bis(o-nitrophenyl)carbonate 154 with aliphatic amines 4 under mild reaction
conditions (Scheme 116).
Scheme 111.
Chaudhari and co-workers have reported the synthesis of carbamates206 6 through the reaction of various organic carbonates
(RMe, 110; RPh, 132; REt, 139) with various amines 4, using
various catalysts (Scheme 112). Out of the several catalysts used, din-butyltin oxide was found to be the best in affording good yields of
the carbamates.
Scheme 116.
Later, Selva and co-workers have reported211 a high-yielding, onepot synthesis of methyl carbamates 6 from primary aliphatic amines
4 and dimethyl carbonate (110) using supercritical CO2 (Scheme 117).
The pressure of CO2 largely inuences both the reaction conversion
and the selectivity towards urethanes. Generally, conversion goes
through a maximum (70e80%) in the mid-range (40 bar) and drops at
lower and higher pressures, whereas selectivity is continuously improved (from 50 up to 90%) by an increase of pressure.
Scheme 112.
Shen and Jiang have reported207 a facile synthesis of N-methyl

N-aryl carbamates from aromatic amines 4 and DMC (110) in the
Scheme 117.
35
Deng and co-workers have reported212 the synthesis of carbamates 6 and dicarbamates 156 through the reaction of variety of
aliphatic amines 4 and bis-amines 155 with dimethyl carbonate 110
catalysed by acid-functionalised ionic liquids (Scheme 118). They
found that eSO3H functionalised ionic liquids were the most effective among the applied ionic liquids.
Scheme 122.
Scheme 118.
Scheme 123.
Later, Li and co-workers have reported213 the synthesis of

methyl phenyl carbamates 6 through the reaction of dimethyl
carbonate (110) with 1,3-diphenyl urea 157 under atmospheric
pressure (Scheme 119). Among the various catalysts that were
used, NaOMe was found to be best in affording high yields of
carbamates.
N-Heterocyclic carboxymethylation of amines 4, using DMC

(110) catalysed by an ionic liquid, afforded the corresponding
carbamates 6 in high yields, reported by Gao and co-workers
(Scheme 124).218
Scheme 119.
Han and Porco have reported214 an efcient protocol for the

synthesis of structurally diverse carbamates 6 through the reaction
of various amines 4 with variety of carbonates (110, 132, 139 etc.)
using a zirconium(IV)-catalysed exchange process with 2hydroxypyridine as a catalytic additive (Scheme 120).
Scheme 124.
Recently, Sureshbabu and Hemantha have reported219 the synthesis of dipeptidyl carbamates 162 through the reaction of an
amino acid 161 with their synthesised F-moc aminoalkyl pentauorophenyl carbonate 160. They have further explored the utility
of 160 in the synthesis of oligopeptidyl carbamates using a variety
of amino acids (Scheme 125).
Scheme 120.
The use of DMC (110) in the synthesis of methyl phenyl carbamates 6 using aromatic amines and an ordered AISBA-15 catalyst
was recently reported by Halligudi and co-workers (Scheme 121).215
Scheme 125.
Recently, an efcient preparation of N-tert-butyl carbamates 6 of

various amines 4 using di-tert-butyl dicarbonate 136 in the presence of Amberlyst 15 under solvent-free conditions was reported
by Pal and co-workers (Scheme 126).220
Scheme 121.
Recently, Yoshida and co-workers have reported216 an efcient

protocol for the synthesis of 5-vinylideneoxazolidin-2-ones 159 by
a DBU-mediated CO2-xation reaction of 4-(benzylamino)-2butynyl carbonates/benzoates 158 (Scheme 122).
The use of DMC (110) was further explored in the synthesis of
methyl N-phenyl carbamates 6 from aromatic amines 4 catalysed
by a ZnOeTiO2 catalyst (Scheme 123).217
Scheme 126.
More recently, an efcient and chemoselective protocol for the

preparation of N-tert-butyl carbamates 6 of various amines 4 using
di-tert-butyl dicarbonate 136 in the presence of tungstophosphoric
acid (TPA)-supported ordered mesoporous silica (SBA-15) under
36
solvent-free conditions was reported by Karmakar and Banerji

(Scheme 127).221
Scheme 127.
Recently, A direct conversion of various allylic imines 164 into

their corresponding a-ethoxy carbamates 166 using diethyl pyrocarbonate 165 was reported by Grognec and co-workers (Scheme
128).222 The imines were synthesised from the corresponding aldehydes 163 using allylic amines 4.
Scheme 130.
Scheme 131.
be converted into carbamates 6 through a one-step synthesis

(Scheme 132).
Scheme 128.
Iwasaki and co-workers have reported223 the synthesis of hydroxy carbamates 6a and 6b from cyclic ve-membered carbonates
167 and primary amines 4 at room temperature (Scheme 129).
Scheme 132.
Scheme 129.
3.6. Carbamate synthesis from dithiocompounds

3.6.1. Using dithiocarbamates/thiocarbamates. Tandel and coworkers have reported an efcient synthesis of carbamates 6
from dithiocarbamates 168 through either a series of transformations via 169 and 170 or direct conversion using NaOMe/
MeOH (Scheme 130).224 The overall yield of carbamates from dithiocarbamates during three steps is 36%, whereas the direct conversion afforded a 95% yield.
Recently, Fochi and co-workers have reported an efcient protocol for the synthesis of various kinds of carbamates 6 through the
reaction of the corresponding thiocarbamates 170 with alcohols 5
in triethylamine (Scheme 131).225
3.6.2. From carbon-imido dithiolates. Rajappa and co-workers have
reported226 that carbon-imido dithiolates 171 are important precursors for the synthesis of carbamates 6 and can be rst converted
into S-methyl thiocarbamates227 172 using zeolite-catalysed partial
hydrolysis. This method therefore provides an alternative route to
methyl carbamates 6.228 The carbon di-imido dithiolates can also
3.7. Carbamate synthesis through rearrangement reactions

3.7.1. Hoffmann rearrangement. Generally, the Hoffmann rearrangement229 converts primary carboxamides into amines using
aqueous NaOH and Br2. In recent years, it has been used for the
synthesis of carbamates 6 through the involvement of an isocyanate intermediate. Several researchers have focused their efforts
on this rearrangement reaction in order to achieve an efcient
synthesis of carbamates.
Moriarty and co-workers have reported230 an efcient protocol
for the synthesis of methyl carbamates 6 from primary alkyl and
aryl carboxamides 173 using hypervalent iodine. They have treated
a series of primary alkyl/aryl carboxamides 173 with PhI(OAc)2 in
KOHeMeOH at 5e10 C to afford the corresponding methyl carbamates 6 in good-to-excellent yields (Scheme 133). These
Scheme 133.
conditions avoid the use of elemental bromine or heavy metal reagents, such as Pb(OAc)4, AgOAc and Hg(OAc)2, while taking advantage of the commercial availability of PhI(OAc)2.
Later, Huang and Keillor have reported231 synthesis of methyl
carbamates 6 via a modied Hoffmann rearrangement. They have
treated a series of p-substituted aromatic and primary aliphatic
carboxamides 173 with NBS and NaOMe in methanol heated to
reux for 10 min for the conversion of the carboxamides into their
corresponding primary amino methyl carbamates 6 in nearly
quantitative yields (Scheme 134). The mild oxidative conditions of
this modied Hoffmann rearrangement are shown to be particularly useful for the preparation of p-substituted anilines.
37
Hiegel and Hogenauer have reported235 a base-catalysed synthesis of N-substituted carbamates 6 through the rearrangement of
N-chloroamides (Scheme 138). These N-chloroamides were obtained by the chlorination of amides 173 using trichloroisocyanuric
acid (TCICA).
Scheme 138.
Nishikawa and co-workers have reported the synthesis of

carbamates 6 through the rearrangement reaction of trichloroacetamides 174 using variety of alcohols 5 (Scheme 139).236
Scheme 134.
They have further elaborated232 the synthesis of methyl carbamates 6 through the involvement of a Hoffmann rearrangement
using NBS and DBU in methanol (Scheme 135). This method has
been widely used for the conversion of alkyl and aryl carboxamides
173 into their corresponding methyl carbamates 6 in excellent
yields under extremely mild conditions.
Scheme 139.
Gogoi and Konwar have reported237 a synthesis of methyl carbamates 6 through a modication of the Hoffmann rearrangement.
Thus, a series of methyl carbamates 6 were synthesized in good-toexcellent yields using NaOCl as an oxidant in the presence of KF/
Al2O3/MeOH under reux conditions (Scheme 140).
Scheme 135.
The synthesis of N-tert-butoxy carbamates 6 from primary carboxamides 173 using a copper(II) reagent (prepared from copper(II)
bromide and lithium tert-butoxide, i.e., CuBr2eLiOtBu), affording
good-to high-yields, has been reported by Yamaguchi and coworkers (Scheme 136).233
Scheme 140.
A recent method for the synthesis of carbamates 6, starting from

the corresponding amines 173 through a Hoffmann rearrangement
using a microreactor technique has been reported by Ley and coworkers (Scheme 141).238
Scheme 136.
Later, Matsumara and co-workers have reported234 the electrochemical synthesis of carbamates 6 from primary carboxamides
173. The process has been referred to as an electrochemically induced (EI) Hoffmann rearrangement, which was developed using
new solvent systems containing a variety of alcohols 5, the reaction
proceeding under mild conditions (neutral). An epoxy functional
group in the amide and alcohol remains intact during the electrolysis (Scheme 137).
Scheme 137.
Scheme 141.
3.7.2. Curtius rearrangement. The Curtius rearrangement involves

the pyrolysis of acyl azides 175 to yield isocyanates 13 (Scheme
142).239 Isocyanates 13 can be treated with alcohols 5 to afford
the corresponding carbamates 6. In recent years, much interest has
been developed among the chemists to synthesise carbamates
through the Curtius rearrangement by trapping of the isocyanate
intermediate 6 with an alcohol 5.
Richer and Andersen have reported240 the synthesis of carbamates 177 in excellent yields using a solid-supported polystyrene
resin. They have prepared an acid azide derivative 176, which was
38
Scheme 142.
previously loaded on to a polystyrene resin and treated with the

appropriate alcohol in m-xylene (Scheme 143).
Scheme 146.
3.7.3. Lossen rearrangement. The Lossen rearrangement is a useful

chemical reaction in which O-activated hydroxamic acids 179 can
be converted into the corresponding isocyanates 13 (Scheme
147).239b,248 Carbamates can be synthesised through in situ trapping of the isocyanate intermediate 13 with an alcohol 5. In recent
years, based on the above concept, researchers have become interested in synthesising carbamates using hydroxamic acids
through the Lossen rearrangement reaction.
Scheme 143.
Lebel and Leogane have reported241 an efcient protocol for the

preparation of tert-butyl carbamates 6 from the corresponding
acids 178. The reaction of carboxylic acids 178 with di-tert-butyl
dicarbonate 136 and sodium azide allowed the formation of the
acyl azides 175, which undergo a Curtius rearrangement in the
presence of tetrabutylammonium bromide and zinc(II) triate to
afford the corresponding carbamates 6 through trapping of the
isocyanate intermediate (Scheme 144). They have extended the
same protocol to the direct synthesis of carbamates of aromatic
amines using aromatic acids.242,243
Scheme 147.
Recently, Papot and co-workers have reported an efcient synthesis of carbamates 6 through the reaction of a hydroxamic acid
179 with an alcohol 5 promoted by 2,4,6-trichloro-1,3,5-triazine
180 (cyanuric chloride; TCT) in the presence of an excess of Nmethyl morpholine (NMM) through Lossen a rearrangement reaction (Scheme 148).249
Scheme 144.
Dussault and Xu have reported a direct conversion of various

acid azides 175 into their corresponding carbamates 6 through
a Curtius rearrangement using ethanol 5 (Scheme 145).244 A similar
kind of approach was adopted by Saigo and co-workers for the
synthesis of fullerene carbamates through the reaction of the corresponding fullerene acid azide with an alcohol.245
Scheme 148.
A recent method for the synthesis of carbamates 6 through the

reaction of hydroxamic acids 179 with an alcohol 5 using N,N0 carbonyl di-imidazole (CDI) through a Lossen rearrangement was
reported by Dube and co-workers (Scheme 149).250
Scheme 149.
Scheme 145.
3.8. Miscellaneous methods

Iklegami and co-workers have reported a synthesis of carbamates 6 of various sugar and other functionalities using the corresponding acids 178. In situ conversion of acids 178 to the
corresponding azides 175 was achieved using diphenyl phosphoryl
azide (DPPA), followed by the addition of an alcohol to afford the
corresponding carbamates (Scheme 146).246 They have further
explored this methodology for the synthesis of carbamate-linked
glycoconjugates using various kinds of sugar acids and DPPA.247
3.8.1. Carbamate synthesis using carbonyl di-imidazole. Fischer has

reported the synthesis of imidazole carbamates 6 through the reaction of N,N-carbonyl di-imidazole 180 (CDI) with variety of alcohols 5 under very mild conditions (Scheme 150).251
The use of imidazolium salt 181 as better leaving group during
the reaction with an alcohol 5 to afford carbamates 6 in high yields
was reported by Batey and co-workers (Scheme 151).252
39
diols 186 using a methyl Burgess reagent 185 (RMe) (Scheme

154).
Scheme 150.
Scheme 154.
Later, Wood and co-workers have reported259 a novel, one-step

conversion of primary alcohols 5 into carbamate-protected amines
6 using a benzyl Burgess reagent 185 (RBn) (Scheme 155).
Scheme 155.
Scheme 151.
3.8.2. Carbamate synthesis using sodium cyanate. Recently, the use

of sodium cyanate 182 in the synthesis of primary carbamates 6
through the reaction with alcohols 5 using various kinds of acidic
catalysts, such as trichloroacetic acid, silica supported-sufuric acid,
silica supported-perchloric acid and Al(HSO4)3 has been realised by
Modaressi-Alam and co-workers (Scheme 152).253e256
Conversion of BayliseHillman adducts 188 of b-amino acids into

the corresponding methyl carbamates 189 using a methyl Burgess
reagent 185 was reported by Mamaghani and Badrian (Scheme
156).260
Scheme 156.
Scheme 152.
3.8.3. Carbamates synthesis using Burgess reagent. The Burgess reagent257 185 is prepared from a reaction of an alcohol 5 with
chlorosulfonyl isocyanate 183 and triethylamine 184 (Scheme 153)
and has been shown to be efcient for the stereospecic cisdehydration of secondary and tert-alcohols to provide olens. Primary alcohols do not undergo elimination, due to a competing (and
predominant) displacement reaction to form the corresponding
methyl carbamates. Several kinds of alcohols have been used, in
order to obtain a more efcient Burgess reagent, which could afford
carbamates in high yields. In recent years, researchers have directed their efforts to synthesising carbamates through the Burgess
reagent.
3.8.4. Carbamate synthesis through transcarbamoylation. A reagent

for mediating the conversion of one carbamate compound into its
higher or lower homologue is known as transcarbamoylating reagent
and the reaction is referred to as a transcarbamoylation reaction. The
transcarbamoylation reaction has important industrial applications
in the eld of polyurethane chemistry, especially for coatings.261 In
recent years, many researchers have directed their efforts for synthesising carbamates through the transcarbomoylation approach.
Rannard and Davis have reported262 an efcient synthesis of
carbamates of higher bis-amines, such as 190 through the reaction
of imidazole carbamate 6 with bis-amines, e.g., 191 (Scheme 157).
Scheme 157.
Scheme 153.
Nicolaou and co-workers have reported258 an efcient, one-pot

synthesis of methyl carbamates 187 through the corresponding cis-
Later, Jousseaume and workers have reported263 the conversion

of a carbamate into its higher homologue using bismuth catalysts
for transcarbamoylation (Scheme 158). They have further studied
the effect of various catalysts (e.g., Bi, Sn, Sc, Sm, Yb, La) on the yield
of the transcarbamoylated product and observed that bismuth
compounds gave very good yields.
40
various catalysts and found that better yields may be obtained

using PbO.
Scheme 158.
Prenyl carbamates 6 have been synthesised by Vatele through

the reaction of prenyl imidazole carbamate 192 with various
amines 4 (Scheme 159).264
Scheme 163.
Yang and co-workers have reported the synthesis of methyl

carbamates 6 from urea 194 and methanol 5 using a variety of
catalysts (Scheme 164).268
Scheme 164.
Scheme 159.
Later, Li and co-workers have reported the synthesis of methyl

N-phenyl carbamate 6b through the reaction of aniline 4 with
methyl carbamate 6a in the presence of a catalyst (Scheme 160).265
They have optimised the activity of various catalysts and found that
ZnCl2 was the best of those studied.
Qin and co-workers have reported269 the synthesis of phenyl

methyl carbamates 6 through the reaction of aniline 4, urea 194
(RH) and methanol 5 using various kinds of catalysts (Scheme
165). They have realised that KNO
3 modied zeolite HY gave the
best yields of carbamates.
Scheme 165.
Scheme 160.
Recently, Shimizu and Sodoeka have reported the synthesis of

various structurally diverse carbamates 6 through the reaction of
a variety of amines 4 with 1-alkoxycarbonyl-3-nitro-1,2,4-triazoles
193 (Scheme 161).266
Scheme 161.
3.8.5. Carbamate synthesis using ureas and alcohols. In recent years,

the synthesis of carbamates has been achieved through the reaction
of ureas with alcohols using various catalytic systems. Thus,
Chaudhari and co-workers have reported the synthesis of carbamates 6 through the reaction of substituted ureas 194 with alcohols
5 using various catalysts (Scheme 162).206 They have optimised the
activity of various catalysts and found that better yields may be
obtained using di-n-butyltin oxide (DBTO), Bu2SnO.
3.8.6. Carbamate synthesis from carbonyl compounds. Tomkinson

and co-workers have rst reported the synthesis of a-carbamates
197 through the reaction of various kinds of carbonyl compounds
196 with N-methyl-O-carbamoyl-hydroxylamine hydrochlorides
195 (Scheme 166).270
Scheme 166.
Seijas and co-workers have reported a solvent-free protocol for

the synthesis of enol carbamates 199 through the reaction of various kinds of carbonyl compounds 196 with N,N-diisopropyl carbamoyl chloride 198 (Scheme 167).271
Scheme 167.
Scheme 162.
Later, Wang and co-workers have reported the synthesis of

methyl N-phenyl carbamate 6 using phenylurea 194 (R1Ph) and
methanol (Scheme 163).267 They have optimised the activity of
Recently, Nair and co-workers have reported the synthesis of Nacyl carbamates 203 through the reaction of substituted aldehydes
200 with dialkyl azodicarboxylates 201 and triphenylphosphine
202 (Scheme 168).272
41
utility as useful agrochemicals has made further demands for their

synthesis. This important functional-group class, although often
overlooked, has considerable potential and no doubt will offer new
and exciting chemistries in the near future.
Acknowledgements
Scheme 168.
3.8.7. Carbamate synthesis from oximes. Goti and co-workers have

reported the synthesis of various substituted aromatic carbamates
205 through the reaction of a variety of aromatic oximes 204 with
alcohols using methyltrioxorhenium (MTO) and urea-hydrogen
peroxide (UHP) (Scheme 169).273
The author is thankful to the Director, North-East Institute of

Science and Technology (CSIR), Jorhat, for providing the necessary
facilities during the preparation of this manuscript. Author is
grateful to Prof. W. B. Motherwell, for his kind invitation and fruitful
suggestions. The author is also thankful to Mr. Suman K. Sen of IIT
Kharagpur, India, for providing several of the references during the
preparation of the manuscript.
References and notes
Scheme 169.
Recently, Elghamry has reported the synthesis of carbamates 6

through the reaction of oximinoacetoacetates 206 with variety of
aromatic amines 4 under solvent-free conditions (Scheme 170).274
Scheme 170.
4. Conclusions
This review gives a comprehensive survey regarding the synthesis of organic carbamates through the various starting materials
from the beginning to the most recent reports (covering the literature to December 2010). Organic carbamates have clearly been
demonstrated to be extremely useful and stable reagents, exhibiting
unique physical, chemical and biological properties. Furthermore, in
organic synthesis, organic carbamates have been shown to be
powerful instruments serving mainly as protecting groups for
amines, as well as synthons for several other functional-group
manipulations. Organic carbamates have become excellent templates for the formation of CeC and carboneheteroatom bonds.
Organic carbamates have also been utilised in the introduction of
oxygen moieties as well as in the activation of various functional
groups, which allows for a plethora of other applications. Organic
carbamates have frequently been used as synthons for the synthesis
of various kinds of structurally diverse synthetic intermediates,
which have broad applications in drug discovery synthesis. In recent
years, it has been realised by various researchers that the introduction of a carbamate functionality into various biologically
active synthetic/natural/semisynthetic molecules signicantly increases their biological activities. In addition, organic carbamates
have made a great impact in the elds of polymer science, biology
and medicine. Organic carbamates have also been utilised in industry and have thus made their way into everyday life. Their wide
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Biographical sketch
Dr. Devdutt Chaturvedi obtained his Ph.D. degree, in Medicinal Chemistry, from the
Medicinal Chemistry Division of the Central Drug Research Institute (CSIR), Lucknow,
India, under the guidance of Dr. Suprabhat Ray, in 2003. His doctoral work was centred
on the design and synthesis of bioactive molecules using carbamates and related
chemistry by developing novel synthetic methodologies employing cheap and safe reagents, such as CO2/CS2. He worked as a Postdoctoral Fellow (2003e2005) at the University of Georgia, USA. Later, he worked as a Postdoctoral Fellow (2005e2006) at the
Institute of Organic Chemistry, University of Goettingen, Germany. He returned to India
and worked for a short period as a Senior Postdoctoral Fellow (2006e2007) at the Department of Chemistry, Indian Institute of Technology (I.I.T.), Madras and as a Scientist
Fellow (2007e2008) at the Bioorganic Chemistry Division, Indian Institute of Integrative Medicine (CSIR), Jammu. He has worked on several areas of organic synthesis and
medicinal chemistry, such as design and synthesis of novel classes of antidiabetic, antifertility, antitubercular, anti-inammatory, hypolipidemic, anti-HIV/HBV, anticancer,
antimalarial and antimicrobial agents, within which he has investigated various kinds
of structurally diverse synthetic/natural molecules, such as steroids, terpenoids, nucleosides, structurally diverse heterocycles, carbamates and related compounds. He has
published more than 50 research papers (containing more than 500 citations) in reputable international journals and has led 11 patents. He is a reviewer for several leading international journals, such as Tetrahedron Letters, Synlett, Synthesis, Chemistry:
An Asian Journal, European Journal of Organic Chemistry, Journal of Sulfur Chemistry,
Monatshefte fuer Chemie, European Journal of Medicinal Chemistry, Letters in Organic
Chemistry, Current Organic Synthesis, Current Organic Chemistry etc. His work has further been recognised by various kinds of awards, such as the Most Cited Paper Award
(2006e2009) for one of his Tetrahedron Letters publication, Young Scientist Award
(2008e2009) from the Govt. of Uttar Pradesh, Highest Impact Factor Award
(2009e2010) for publishing a review article in Chemical Society Reviews (I.F.26.58)
from the North-East Institute of Science and Technology (CSIR), Jorhat, Assam, India
and DST-Fast Track Young Scientist Award (2010) from the Govt. of India. Recently,
He has worked as a Guest Editor for publishing a hot topic issue entitled Organic Synthesis Using Green Reaction Media for a leading international journal Current Organic
Synthesis (I.F.3.95) published by Bentham Science Publishers, Ltd. He has also been
invited to become a member of editorial board for an international journal, ISRN Organic Chemistry Journal, published by Hindawi Publishers USA. He is presently working
at the Natural Products Chemistry Division of the North-East Institute of Science and
Technology (CSIR), Jorhat, Assam, India on the design and synthesis of novel classes
of bioactive natural/semisynthetic/synthetic molecules for the treatment of various
diseases employing novel synthetic methodologies and has been associated with the
chemistry and biology of organic carbamates for more than a decade.
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Tetrahedron 68 (2012) 15e45

Contents lists available at SciVerse ScienceDirect

Tetrahedron report number 958

Perspectives on the synthesis of organic carbamates

* Corresponding author. Fax: 91 376 2370011; e-mail addresses: ddchaturvedi@rrljorhat.res.in, devduttchaturvedi@gmail.com.

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

anti-HIV, antiestrogenic, antiprogestational, antiosteoporosis, antiinammatory, antilarial, antitubercular, antidiabetic, antiobesity,

Physostigmine: Anti-alzheimer drug

Taxol analogues: anticancer drugs

Linezolid: Antibacterial drug

Telithromycin: Antibacterial drug

Fig. 1. Biologically active drug molecules bearing carbamate linkage.

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

Vitamin D3 carbamate dimer

Fig. 2. Potential anticancer carbamates of various natural products.

carbonates and several other useful synthetic routes. Thus, keeping

triphosgene, which is relatively safer to use.60 Thus, carbamate 6

Carbamates can be mainly classied into two groups, namely

Phosgene (1) is a potentially useful, versatile building block in

Chloroformates and isocyanates are intermediates produced

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

Carbamate conjugate of cephalosporin with oxazolidinones

conditions, such as the use of strong bases8a,62 (NaOH, NaHCO3,

Later, Mormeneo and co-workers have reported66 a versatile

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

phenols) affording the corresponding carbamates is the most

Isocyanates2a,69a 13, obtained through the reaction of phosgene

3.2. Reductive carbonylation of nitroaromatics

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

Several reports have been published by Gladfelter and Cenini

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

Fig. 6. Classication of carbamates.

Very similar results were obtained by Cenini using [(PPh3)2N]

+ 2CO & 2MeOH

of the type [Pd(Py)2Cl2] can catalyse the reaction at a low Py/Pd

Most previously reported catalytic systems for the reductive

R' = Et, tert.Butyl

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

More recently, Tomkinson and co-workers have reported99 an

Later, Shi and co-workers have reported108 a novel synthesis of

Shi and co-workers have reported109 an efcient and clean

Carbamates 6 have been prepared in good-to-excellent yields

3.3. Oxidative carbonylation of amines

The use of iodine promoted by a Pd catalyst,104 or a gold complex

Recently, Mei and co-workers have reported111 the synthesis of

More recently, the synthesis of N-phenyl carbamates 6 through

Wan and co-workers have reported107 an efcient synthesis of

3.4. Using metal/non-metal carbonates/bicarbonates

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

NH2 + ROH + CO + 1/2 O2

(Cs2CO3) have been used alone and in combination with different

3.5. Synthesis of carbamates using carbon dioxide

The role of Cs2CO3 in minimising the synthesis of N-alkylated

Later, Yoshida and co-workers have also reported123 the

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

Later, Ishii and co-workers have reported124 the synthesis of

Kojima and co-workers have reported129 a carbamate synthesis

Mono-carbamates of 1,2-diols 41 have been synthesised125 from

Toda have reported130 the synthesis of cyclic carbamates

The mono-carbamates 41 could also be obtained,126 starting

This reaction led to the formation of bis(2-oxazolidinones)131 60

D. Chaturvedi / Tetrahedron 68 (2012) 15e45

However, this method was only useful for the preparation of