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J. Iran. Chem. Soc., Vol. 4, No. 2, June 2007, pp. 126-174.

JOURNAL OF THE
Iranian
Chemical Society

Application of N-Halo Reagents in Organic Synthesis

E. Kolvaria, A. Ghorbani-Choghamaranib, P. Salehic, F. Shirinid and M.A. Zolfigol a,*


a
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran
b
Department of Chemistry, Faculty of Science, Ilam University, Ilam, Iran
c
Department of Phytochemistry, Medicinal Plants and Drugs Research Institute,
Shahid Beheshti University, Evin, Tehran, Iran
d
Department of Chemistry, Faculty of Science, Guilan University, Rasht, Iran

(Received 11 April 2007, Accepted 1 May 2007)

This review article summarizes published data on the application of N-halo reagents (such as N-halo amines, N-halo amides
and/or imides, N-halo sulfonamides and/or imides, and etc.) in various organic functional group transformations such as:
oxidation reactions, deprotection and protection of different functional groups, halogenation of saturated and unsaturated
compounds, acylation of alcohols, phenols, amines or thiols, epoxidation of alkenes, aziridination and etc. The main purpose of
writing this review is encouraging of active researchers interested to this field for the synthesis of new N-halo reagents specially
with different halogens and applications of these new N-halo reagents in organic reactions or finding more and more applications
of existing N-halo reagents in organic synthesis.

Keywords: N-Halo reagents, N-Halo imides, N-Halo amines, N-Halo sulfonamides, N-Halo amides, N-Halo sulfonimides

This article is dedicated to Professor Seyyed Ahmad Banihashemi one of the founders of polymer chemistry in Iran on the
occasion of his 75th birthday.

INTRODUCTION application of such compounds is so wide that all N-halo


reagents can not be considered within the framework of a
Synthetic methodology, as the building block of organic single review article, but we decide to introduce them briefly
synthesis, continuously seeks for new reagents, better reaction and believe that it may be useful to achieve new idea and
conditions, and more efficient and selective methods. In this applications. In the other way, the chemistry of N-halo
regard, a large group of compounds entitled N-halo reagents reagents was the subject of several review articles [1-8].
are widely used in fine organic synthesis. These include N- However, since that time numerous new data has been
halo derivatives of amines, amides, imides, urea, saccharines, appeared in the literature which are summarized in the present
sulfonamides, sulfonimides, and etc. Although the scope of the review. Some specific features of N-halo reagents such as high
activity of the N-X bond and various modes of its splitting,
*Corresponding author. E-mail: zolfi@basu.ac.ir determine their wide application in organic synthesis.
Kolvari et al.

Depending on the conditions, a number of highly reactive few hours under mild conditions [13].
intermediates can be formed including halogen radicals, The enantioselective epoxidation of chalcones was carried
halogen cations, halogen anions, N-radicals, N-cations, N- out using TCCA as oxidant in the presence of a chiral
anions, etc. Consequently, N-halo reagents have the potential quaternary ammonium salt as a phase transfer catalyst in good
to promote important reactions such as halogenation, yields with moderate enantiomeric excesses (Scheme 1) [14].
oxidation, and protection as well as formation of C-X, C-O,
and C=O bonds. In addition to the numerous organic and
inorganic halogenating agents, N-halo reagents play an R1 H

especially important role in the chemistry of natural


H N
compounds. Some of the N-halo reagents which are presented
in Tables 1-4 are reviewed in this article.
OR2

TRICHLOROISOCYANURIC ACID O 10 mol% O O


R R' R R'
Trichloroisocyanuric acid (TCCA, 1), 1,3,5-trichloro- Toluene, TCCA, 50% KOH

1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione, was first synthesised R = Ar, R' = Alkyl or Aryl
in 1902 from the reaction of the potassium salt of cyauric acid
with chlorine gas [9]. TCCA was commonly named as
Scheme 1
Symclosene, ACL-85 and Chloral [10,11].
TCCA was used in the presence of base as an efficient
O
oxidant for the epoxidation of enones and tandem oxidation-
Cl Cl epoxidation of allylic alcohols in a water suspension system in
N N
the presence of a surfactant (Scheme 2) [15].
O N O
Cl
1
O O O
TCCA
1
R1 R2 R R2
Surfactant, KOH(aq)

The worldwide production of TCCA is considerably R1, R2= Aryl or Alkyl


increased for its purpose as disinfecting swimming pools, Scheme 2
cleaning and sterilizing bathrooms and using in laundry.
Recently, TCCA has found many uses in organic synthesis. The preparation of epoxides was efficiently achieved by
The application of TCCA in organic transformations was the reaction of alkenes with TCCA in aqueous acetone
reviewed in 2002 extensively by Tilstam and Wienmann [12]. followed by treatment of the resulting chlorohydrin with
Herein the application of TCCA in organic synthesis is aqueous KOH in ether/pentane (Scheme 3) [16].
reviewed from that time.

Oxidation Reactions R1 R1 OH R1 O
TCCA KOH
Oxidations by TCCA are mainly categorized into two Surfactant, KOH(aq) Cl R2 R3
R2 R3 R2 R3 Et2O, Pentane, r.t.
sections, transfer of oxygen and dehydrogenation. An
R1 = Aryl or Alkyl, R2, R3 = H or Alkyl
interesting application of TCCA is the conversion of ,-
unsaturated carbonyl compounds to their corresponding
epoxides. TCCA has been used for the oxidation of enones in Scheme 3

127
Application of N-Halo Reagents in Organic Synthesis

Table 1. The Name and Structure of N-Bromo Reagents

Name Abbreviate name Structure


O

N-Bromosuccinimide NBS N Br

O
O
Br Br
N N
Tribromoisocyanuric acid TBCA
O N O
Br
O
Br
N N
Sodium monobromo isocyanurate SMBI
O N O- Na+
H
O

1,3-Dibromo-5,5-dimethylhydantoin DBDMH, DBH Br N


N
Br
O
O

N-Bromophthalimide NBPI N Br

O
O Br
N-Bromo-p-toluenesulfonamide sodium salt
- H3C S N
(Bromoamine T) -
+
O Na
O

N-Bromosaccharin NBSa N Br
S
O
O
H3C
N,N'-Dibromo-N,N'-1,2-ethanediyl -bis (p-
BNBTS SO2NCH2 )
toluenesulfonamide) 2
Br

N,N,N',N'-Tetrabromobenzene-1,3- Br2N NBr2


TBBDA S S
disulfonamide
O O O O

H3C SO2
N-Bromo bis(p-toluenesulfonyl)amine NBBTA N Br
H3C SO2

128
Kolvari et al.

Table 1. Continued

Poly N-bromo benzene-1,3- Br Br


PBBS ( H2C N N CH )
sulfonamide S S 2 n

O O O O

O O

1,3-Dibromo-5,5-diethylbarbituric acid - N N
Br Br
O

Table 2. The Name and Structure of N-Chloro Reagents

Name Abbreviate name Structure

N -Chlorosuccinimide NCS
N Cl

O
O
Cl Cl
N N
Trichloroisocyanuric acid TCCA
O N O
Cl
O
Cl
N N
Sodium dichloroisocyanurate SDCI
O N O- Na+
Cl
O

1,3-Dichloro-5,5-dimethyl hydantoin DCDMH, DCH Cl N


N
Cl
O
O

N -Chlorophthalimide NCPI N Cl

O
O Cl
N-Chloro-p-toluenesulfonamide
- H3C S N-
sodium salt (Chloramine T) Na+
O
O

N -Chlorosaccharin NCSac N Cl
S
O
O

129
Application of N-Halo Reagents in Organic Synthesis

Table 2. Continued

NHCl

Trichloromelamine TCM N N

ClHN N NHCl

2-Nitro-N,N'-dichloro-benzensulfonamide 2-NsNCl2 NO2


O S O
NCl2
Cl

N
2,6-Dichloropyridazin-3(2H)-one - N
Cl
O
Cl Cl
N,N,2,3,4,5,6-Heptachloroaniline N
Cl Cl
-
Cl Cl
Cl
(CH-CH2)
n
Poly[4-vinyl-N,N'-dichlorobenzenesulfonamide]
-
SO2NCl2

Table 3. The Name and Structure of N-Flouro Reagents

Name Abbreviate name Structure


R3
R2 R4
N-Flouropyridinium salts - 5
R1 N R
F X-
R
N
1-Alkyl-4-fluro-1,4-diazabicyclo
-
[2,2,2]octane N
F (X)
2

N-Fluoroquinuclidinium
- N
tetrafluoroborate
BF4
F
O
O
N-Fluoro-3-cyclohexyl-3-methyl-2,3- S
dihydrobenzo[1,2-d]isothiazole-1,1- CMIT-F NF

dioxide Me

130
Kolvari et al.

Table 3. Continued

O O
S
N-Fluoro-3-ethyl-3-methyl-1,1-dioxo-2,3- NF
- Me
dihydro-16-benzo[e]1,2-thiazin-4-one
Et
O

R
R
N-Fluorocamphorsultam -
N
O S F
O
O O
S
N-Fluoro-o-benzenedisulfonimide NFOBS N F
S
O O
CH2Cl
N
1-(Chloromethyl)-4-fluoro-1,4-diazabicyclo
F-TEDA-BF4
[2,2,2]octane bis(tetrafluoroborate)
N
F
O O
Ph S
N-Fluorobenzensulfonimide NFSi N F
Ph S
O O
NO2
N
N-Flouro-2,4-dinitroimidazole NF-2,4-DNI N F
O2N
O O
F3C S
N-Flouro bis[(trifluoromethyl)sulfonyl]imide - N F
F3C S
O O
O O
S
N
N-t-Butyl-N-flurobenzensulfonamide -
F

Table 4. The Name and Structure of N-Iodo Reagents

Name Abbreviate name Structure


O

N-Iodosuccinimide NIS N I

131
Application of N-Halo Reagents in Organic Synthesis

Table 4. Continued

N-Iodophthalimide NIPI N I

O
O

N-Iodosaccharin NISac N I
S
O
O
H 3C
N,N'-Dibromo-N,N'-1,2-ethanediylbis(p-
BNITS SO2NCH2 )
toluenesulfonamide) 2
I

O R3 OH R3

Cl Cl R2 R2
N N N N
+ AcOH, NaOAc +
O N O R 4
N R 1 CH3CN, CH2Cl2, H2O HO N OH R4 N R1

Cl O

R1 = H, Methyl, Vinyl, Cl, R2 = H, Methyl, Vinyl


R3 = H, Methyl, Vinyl, R4 = H, Methyl

Scheme 4

Oxygen transfer to nitrogen was also achieved by TCCA. TCCA was successfully used for the synthesis of Fipronil
Pyridine and its derivatives were readily oxidized to their N- 2 (a highly efficient insecticide) from the corresponding
oxides with a solution of TCCA, acetic acid, sodium acetate sulfide (Scheme 6) [19].
and water in acetonitrile and dichloromethane with 78-90%
O
yields (Scheme 4) [17]. CH3 CH3
F3C S F3C S
Acetylenic sulfides were oxidized to acetylenic sulfoxides
N N
by a solution of pyridine, water, benzoic acid and TCCA in H2N
N
H2N
N
TCCA
acetonitrile and dichloromethane (Scheme 5) [18].
CH3CN, CH2Cl2, H2O
1h, 70%

O CF3 CF3
TCCA, Py
R1 C C S R2 1
R C C S R2 2
CH3CN, CH2Cl2, H2O
82-94% Scheme 6
R1 =Ph, n-C3H7, n-C4H9, n-C6H13, n-C5H11, -CH2OCH3
R2 = Ph, 4-MeC6H4
The second oxidation mechanism by TCCA involves
Scheme 5 dehydrogenation. This behavior may be applied for the

132
Kolvari et al.

aromatization of cyclic compounds or oxidation of alcohols, TCCA was used for the oxidation of urazoles and bis-
primary amines and hydrazines. TCCA was used for the urazoles to their triazolinediones under both heterogeneous
oxidation of 1,3,5-trisubstituted pyrazolines to their and also solvent-free conditions with excellent yields at room
corresponding pyrazoles under either heterogeneous or temperature (Scheme 10) [24].
solvent-free conditions in good yields at room temperature
(Scheme 7) [20].
R1 H
N N TCCA N N
CH2Cl2, r.t.
R2 N 1 O N O or solvent- free O N O
N R R2 N R1
TCCA N R 2
R 2

CCl4, r.t. 1 2
R 3
or solvent-free R = H or Na, R = Alkyl or Aryl
R3
R1, R2, R3 = Aryl
Scheme 10
Scheme 7

Dehydrogenation of 1,2-bis(cyanoalkyl)hydrazines for the


Similar reactions were carried out under microwave synthesis of azobisnitriles was reported by Mohite, et al. by
irradiation in acetic acid [21]. Dehydrogenation of a variety of the use of TCCA in acetonitrile at room temperature (Scheme
2-imidazolines to the corresponding imidazoles was achieved 11) [25]. Azobisnitriles are an important class of compounds
by TCCA in the presence of DBU (Scheme 8) [22]. that are widely used as initiators in free radical polymerization
Chemoselective oxidation of these compounds was reactions.
successfully carried out in the presence of sulfides and
alcohols.
CN CN CN CN
H H TCCA
R1 C N N C R1 R1 C N N C R1
CH3CN, r.t.
N TCCA, DBU N R2 R2 R2 R2
R CH3CN, -15 C, 3 min R R1, R2= Methyl, Ethyl, n-Propyl, or R1=R2= -(CH2)4-, -(CH2)5-
N N
H H
R= Alkyl or Aryl Scheme 11

Scheme 8
An interesting application of TCCA was reported by
Chen and his co-workers reported the oxidation of primary Hieagl, et al. in the conversion of -aminoacids into nitriles
amines into nitriles by TCCA in the presence of a catalytic by oxidative decarboxylation in water or methanol in the
amount of TEMPO under mild reaction conditions (Scheme 9) presence of pyridine [26]. For example L-isoleucine was
[23]. Optimization of the reaction condition showed that the converted to (S)-(+)-2-methylbutyronitrile in 88% yield after
best results were obtained in dichloromethane at 10 C and the 3.5 h with no considerable loss of its optical purity (Scheme
use of 1 mol% of the catalyst. 12).

TCCA, TEMPO(1mol%) H NH2


RCH2NH2 RCN
CH2Cl2, 10 C O TCCA, Py CN
1.5-4 h, 80-91 % H2O, 3.5 h
H OH H
R = Alkyl or Aryl 88%

Scheme 9 Scheme 12

133
Application of N-Halo Reagents in Organic Synthesis

TCCA takes part in dehydrogenation of primary and procedure and the total absence of any transition metal make
secondary alcohols for their conversion to aldehydes and the reaction suitable for safe laboratory use (Scheme 15). A
ketones, respectively. Chemoselective oxidation of benzylic mechanism was proposed for these reactions (Scheme 16).
and secondary alcohols was achieved by the use of TCCA and
Boc Boc
wet SiO2 in the presence of a catalytic amount of KBr under
N N
heterogeneous conditions at room temperature (Scheme 13)
TCCA
[27]. TEMPO(cat.), NaBr
N acetone, NaHCO3 N CO2H
Boc OH r.t., 24 h, 100% Boc
O
O H2O Cl Cl
N N
R1 R2
HOCl Scheme 15
O N O
Br O Cl
H H
N N
O N O
Br TCCA
H
N N
OH
O O Cl
Cl + OH R OH
R1 R2
O
Cl
1 2
R , R = Aryl and Alkyl N NH
O N O N
Cl
Scheme 13 O O
O
Cl Cl H R
H2O N N H
In some examples TCCA has been used for the oxidation O N O
of primary alcohols to carboxylic acids. For instance, by the Cl H
R O
combined use of catalytic RuCl3 (1.0 mol%) and stochiometric N
amount of TCCA in the presence of n-Bu4NBr and K2CO3, O O OH
Cl O
smooth oxidation of primary alcohols to carboxylic acids was N NH R H
HOCl HCl
O N O R OH
occurred [28]. Secondary alcohols were oxidized to ketones H
using a similar set of reagents. The method is mild and permits Scheme 16
the chemoselective oxidation of alcohols in the presence of
other sensitive functional groups such as vinyl and ketals Fluorinated alcohols were also oxidized to aldehydes by
(Scheme 14). the use of TCCA in the presence of TEMPO [30]. TCCA was
used for the conversion of primary alcohols and diols to
O
O methyl esters and lactones, respectively, by refluxing in
O
O O dichloromethane (Scheme 17) [31].
OH O
O
TCCA
n-Bu4NBr, K2CO3 O O O
O O
CH3CN/H2O
52% OH TCCA OMe
CH3OH, CH2Cl2
Scheme 14 24 h, 99.6%

O
Efficient oxidation of primary alcohols to the OH TCCA
corresponding carboxylic acids was carried out at room O
OH Py, CH2Cl2
5 h, 97%
temperature and in acetone/water, using TCCA in the presence
of a catalytic amount of TEMPO [29]. The mild conditions of Scheme 17

134
Kolvari et al.

Chlorination Reactions Chlorination of nitrogen containing -deficient


TCCA was efficiently used for a series of chlorination heteroaromatics was achieved by a similar reagent system in
reactions of different compounds such as amines, amides, toluene (Scheme 21) [36].
alkenes, alkynes, aromatic rings, alcohols, carbonyls and etc.
The reaction between amines or -aminoacids with TCCA
Cl
was studied under various conditions; N,N-dichloroamines, O
nitriles and ketones could be obtained from primary amines, NH TCCA, Ph3P N
while free aminoacids underwent oxidative decarboxylation to toluene, Reflux
N 3.5 h, 89% N
the corresponding nitriles of one less carbon atom (Scheme
18) [32]. Scheme 21

TCCA
RNH2 RNCl2
CH2Cl2, 15 C
Regioselective chlorination of isatin at the 5-position and
R NH2
TCCA RCN
also deactivated aromatic compounds, such as nitrobenzene
Et3N, DMF was carried out by TCCA in H2SO4 [37]. An interesting
15 C
CO2H example of application of TCCA as a chlorinating agent was
TCCA
RCN described in the synthesis of some cyclic dichloroimines
R NH2 NaOH, H2O
5 C (Scheme 22) [38].
R= Aryl or Alkyl

Scheme 18 R R

N
N-Chlorination of various amides, lactams and carbamates TCCA N
Br CHCl3/CH3CN
were proceeded efficiently by TCCA under very mild Cl Br
reflux
condition at room temperature [33]. An interesting example Cl
R= H or Cl
that demonstrates the chemoselectivity of the method is shown
Scheme 22
in Scheme 19.

HO HO
TCCA The preparation of diverse -chloroethers, -chloroacetates
Boc Boc
N CO2Me CH2Cl2, r.t. N CO2Me and chlorohydrins was achieved by the reaction of alkenes
H 3 h, 99% Cl with TCCA in alcohols (MeOH, EtOH, i-PrOH and t-BuOH),
acetic acid or aqueous acetone, respectively (Scheme 23) [39].
Scheme 19

A similar protocol was reported for N-chlorination of R3 R3 Cl


primary amides in methanol [34]. TCCA
R2

Hiegel et al. reported a procedure for the conversion of R2 R1 R4OH, r.t. R4O R1

alcohols to alkyl chlorides using TCCA in the presence of R1= Ph, Alkyl R3= H, Methyl
triphenylphosphine (Scheme 20) [35]. R2= H, Alkyl R4 = H, Alkyl, Ac

CH3(CH2)8CH2OH
TCCA, Ph3P
CH3(CH2)8CH2Cl
Scheme 23
CH3CN, 60 C
2 h, 74%
TCCA was reacted with alkynes in the presence of water in
Scheme 20 acetone or acetonitrile to form ,-dichloro ketones and in

135
Application of N-Halo Reagents in Organic Synthesis

methanol to form ,-dichlorodimethyl ketals (Scheme 24) They have also reported an easy and general method for
[40]. deprotection of thioacetals to their corresponding carbonyl
compounds using TCCA/silica gel in the presence of water
O
[45]. Similar reactions were also carried out in non-aqueous
TCCA conditions (CHCl3 and DMSO) at room temperature [46]. The
H2O, acetone Cl Cl
59% same group took advantage of TCCA in catalytic preparation
and cleavage of THP-ethers of various hydroxy functional
H3CO OCH3
groups with high yields (Scheme 27) [47]. A mechanism was
TCCA
Cl Cl
CH3OH
62%
TCCA (cat.), DHP
60-80 C
Scheme 24 ROH
TCCA (cat.), MeOH, r.t. RO O

Carboxylic acids were chlorinated in the -position by R = 1, 2, 3, Allylic, Propargylic, Benzylic

heating with TCCA after formation of a small amount of the Scheme 27


acid chloride using PCl3 [41]. The synthesis of dialkyl
chlorophosphates was described by Acharya et al. from the proposed for these transformations (Scheme 28).
reaction of dialkyl phosphite with TCCA in short reaction
times at room temperature (Scheme 25) [42].

O O
RO TCCA RO RO
P Cl O
P H
RO CH3CN, r.t. RO
10-15 min O
RO O
Cl
R= Phenyl, Benzyl, or Alkyl ROH + N H
ROH
Scheme 25
O
Treatment of styrene-butadiene rubber with TCCA was OR
Cl + N
reported to chlorinated the rubber and improved its adhesion H
H
properties [43,44]. O O

Cleavage and Formation of Carbon-Oxygen and O

Carbon-Sulfur Bonds Scheme 28


TCCA has efficiently been used for the cleavage and
formation of carbon-oxygen and carbon-sulfur bonds. Acylation of primary, secondary and tertiary alcohols was
Firouzabadi et al. reported the trans thioacetallization of achieved by the reaction with acetic anhydride and TCCA at
diacetals of 2,2-bis(hydroxymethyl)-1,3-propanediol in room temperature in good to excellent yields (Scheme 29)
dichloromethane at room temperature (Scheme 26) [45]. [48].

O O S OH OAc
TCCA TCCA
R R R
HS(CH2)nSH n-2 R 1
R 2 Ac2O, CH2Cl2 1
R R2
O O S
CH2Cl2, r.t. r.t.
n = 2, 3
R1, R2 = Alkyl, Aryl
R= Substituted Phenyl, Cinnamyl

Scheme26 Scheme 29

136
Kolvari et al.

A novel and efficient trimethylsilylation of various TCCA and triphenylphosphine in the presence of carboxylic
alcohols and phenols was efficiently carried out with acids resulted in the in situ formation of the corresponding
hexamethyldisilazane (HMDS) in the presence of catalytic acid chlorides [53]. Subsequent addition of amines or alcohols,
amounts of TCCA in good to excellent yields in in the presence of a tertiary amine, afforded the corresponding
dichloromethane at room temperature (Scheme 30) [49]. amides, or esters, in good to excellent yields. The method was
interestingly applied to the synthesis of a protected dipeptide
(Scheme 33).
TCCA (0.06-0.1 mmol),
HMDS (0.8 mmol)
ROH ROSiMe3
CH2Cl2, r.t.
BnO
O O O
R = 1, 2, 3, Benzylic, Naphtyl 1) TCCA, Ph3P, CH2Cl2
0 C to r.t., 45 min
OH N
Scheme 30 NHBoc 2) O NHBoc
N , Et3N, 2 h
85%
H H OBn
Cl
Miscellaneous Reactions
A combination of TCCA and sodium nitrite in the presence Scheme 33
of wet SiO2 has been used for the nitrosation of N,N-dialkyl
amines under mild and heterogeneous conditions [50]. For
example 2-methylpiperidine was converted to its N-nitroso Alcohols were converted into alkyl nitrates, nitrites or
derivative in short time with quantitative yield (Scheme 31). thiocyanates by the action of TCCA and triphenylphosphine
along with silver nitrate, silver nitrite, or sodium thiocyanate,
respectively (Scheme 34) [54].
TCCA, NaNO2
NH N NO
CH2Cl2, wet SiO2
15 min, 99%
TCCA, Ph3P
ROH R-ONO2
CH3CN, AgNO3
Scheme 31
TCCA, Ph3P R-ONO
ROH
CH3CN, AgNO2

TCCA, Ph3P
The same reagent system was used for the mononitration ROH R-SCN
CH3CN, NaSCN
of p-substituted phenols at room temperature in good yields
R= Nonyl, Octyl, Cyclohexyl, Benzyl
(Scheme 32) [51].
Scheme 34
OH OH
NO2
TCCA, NaNO2 Amides were chlorinated on nitrogen using TCCA and the
CH2Cl2, wet SiO2 produced N-chloroamides were then rearranged to the
r.t.
X X corresponding methyl-N-substituted carbamates by sodium
X = F, Cl, CN, CH3, OCH3, COCH3, CHO, CH2Ph, NHOAc, CO2H
methoxide in methanol [55]. Isocyanates were suggested as
the intermediates (Scheme 35).
Scheme 32 TCCA was used efficiently for the synthesis of 3,4-
dihydropyridine-2(1H)-ones through the three-component
Dinitrophenols were also obtained in a similar way but Biginelli reaction of a -ketoester, an aldehyde and urea
under solid-phase reaction conditions [52]. The reaction of (Scheme 36) [56]. TCCA has been used as an initator for the

137
Application of N-Halo Reagents in Organic Synthesis

O O
O
TCCA NaOCH3
R NH2 R N C O R N OCH3
CH3OH R NHCl CH3OH H

R= Substituted Phenyl, Benzyl, Alkyl

Scheme 35
O R1

O O O R 2O NH
R1CHO + + TCCA
OR2 H 2N NH2 O
Solvent-free, 90 C N
H
2h
R1= Alkyl or Aryl, R2= Methyl or Ethyl
Yield: 75-90%

Scheme 36

metal-catalyzed living radical polymerization of methyl An efficient and highly regioselective bromination of
methacrylate [57]. activated aromatic rings promoted by TBCA through in situ
generation of Br+ has been developed by de Almeida et al.
TRIBROMOISOCYANURIC ACID AND [58a]. For example, monobromination of 2-methoxy-
SODIUM MONOBROMOISOCYANURATE naphtalene was carried out in excellent yield after a short
reaction time (Scheme 37). Also, Niknam et al. have reported
There are few reports on the application of
tribromoisocyanuric acid [58a-d] (TBCA, 3) and sodium
Br
monobromoisocyanurate (SMBI, 4) in the bromination of
OCH3 OCH3
aromatic compounds. TBCA
MeOH, r.t.
0.5 h, 90%
O O
Br Br Br Na
N N N N Scheme 37
O N O O N O
nitration of phenols, silylation of alcohols and oxidation
Br H

3 4

Br O

N
O H
CF3CO2H
N
H O
O
SMBI O
O
O Br
N
H
H2SO4
5
O
O

Scheme 38

138
Kolvari et al.

of urazoles using TBCA [58b-d]. (Scheme 40).


A variety of aromatic compounds with both activating and
deactivating substituents were brominated with SMBI [59]. 1,3-DIBROMO-5,5-DIMETHYLHYDANTOIN
Diethyl ether, diethyl ether-methanesulfonic acid,
trifluoroacetic acid or sulfuric acid was employed as solvents. 1,3-Dibromo-5,5-dimethylhydantoin (DBH, 6) with the
Thus, nitrobenzene were conveniently brominated in sulfuric commonly used trade name Brom-55, is a cream to pale-
acid, benzene was readily monobrominated in diethyl ether- brown powder which melts at 186-192 C. This reagent is
methanesulfonic acid and phenol was selectively brominated sparingly soluble in carbon tetrachloride, benzene and water
at the ortho position under milder conditions in refluxing (0.06%, 1.1%, and 0.1% at 20 C, respectively). Due to its
diethyl ether. An interesting example was selective economic advantages, DBH has found widespread
bromination of compound 5 by changing the solvent (Scheme applications in industrial processes such as swimming-pool
38). sanitizer, brominating agent for ethylene propylene diene
Bromination of some azulene derivatives were achieved by monomer rubber (EPDM) to improve ozone resistance,
SMBI. Bromination in dichloromethane gave the products in additive in plastics to promote photodegradation and as a
low yields, while the reactions in dichloromethane-water gave fungicide to preserve fresh fruits [61-68].
good yields of the desired compounds (Scheme 39) [60]. The
following mechanism was suggested for these reactions
Br
O N O

R R
Me N
Me Br
SMBI
CH2Cl2-H2O
6
Br

R = Et, n-Pr, Ac2O Among the methods, which were reported for the
preparation of DBH [69-72], the bromination of 5,5-
Scheme 39 dimethylhydantoin (DMH) in the presence of NaOH or

O
O
Br
N NH Br Br
HN N
O H O
O N O
O N O H H
Na+ H2O
Na+

CO2Me CO2Me CO2Me

Br
H Br
Br
O H-OH2
H

Scheme 40

139
Application of N-Halo Reagents in Organic Synthesis

CO2H CO2H
NaHCO3 was studied with precision (Scheme 41) [73]. It was

R1 DBH (0.55-0.66 eq) R1


R3 Br
NaOH (1.1 eq), r.t., 18-22 h
H Br 90-98% R3 R2
R2
O N O O N O
NaOH Substrate
+ Br2 Product
Me N N
or NaHCO3 Me 1 2 3
R , R , R = 3,4,5-(OMe)3 1 2 3
R , R , R = 3,4,5-(OMe)3, 2-Br
Me H Br
Me R1, R2 = H; R3 = 2-OMe R1, R2 = H; R3 = 2-OMe, 5-Br
R1 = H; R2, R3 = 2,3-(OMe)2 R1 = H; R2, R3 = 2,3-(OMe)2, 6-Br
Scheme 41
Scheme 43
reported that the mechanism of the reaction consists of two
bromination steps (Scheme 42). Studies cleared that the rate of the bromination of various
aromatic derivatives substituted with electron donating groups,
with DBH, considerably enhanced in the presence of
H H trimethylsilyltrifluoromethanesulfonate (TMSOTf) [75]
O N O O N O (Scheme 44).

Step 1: N + NaOH Me N
Me
H Na
Me Me
OMe OMe
2NaOH + Br2 NaOBr + NaBr + H2O OMe
DBH(0.5 eq)
H Br
N
TMSOTf (0.5 eq)
O O O N O r.t., 2 h, 50-86%
Br
Me N + NaOBr N + NaOH Scheme 44
Na Me
Me Na
Me

The authors explained activation of DBH in the presence


Step 2: H2O + Br2 HOBr + HBr of TMSOTf via bromination of triflate, as a reactive
Br Br
intermediate (Scheme 45).
O N O N
O O

Me N + HOBr N + NaOH
Na Me Br Br
Me Me Br H
O N O O N OSiMe3 O N O
TMSOTf
NaOH + HBr NaBr + H2O + TfOH
N Me N NH
Me Me
Me Br Me Me
ArBr
Scheme 42 DMH
+ BrOTf
ArH
The application of DBH in organic reactions mainly can be
studied in the following sections. TMSOTf
DMH

Halogenation Reactions
DBH BrOTf ArBr
Bromination reactions. In 1993, Auerbach and co-
workers reported that DBH in aqueous NaOH can be used as
TfOH Ar
an efficient reagent for the bromination of activated benzoic
acids [74]. They also showed that DBH gave better yields than
Scheme 45
NBS (Scheme 43).

140
Kolvari et al.

Similarly, Eguchi and co-workers used DBH in the pyrogallol derivatives by DBH, which gave single
presence of organic and inorganic acids with pKa values less monobromides in 1.5 h at room temperature (Scheme 48) [78].
than -2 to get the monobromide in excellent yields [76]. Very
good yields were obtained even for aromatics having electron-
COOMe COOMe
withdrawing substituents. In some cases, catalytic amounts of
Br
acids were sufficient (Scheme 46). DBH (0.53 eq)
r.t., 1.5 h, 77%
O OH O OH
O O
R R Me Me
Me Me
DBH/acid (0.5/(0.1-1.0 eq)) Scheme 48
r.t. or reflux, 5 min-24 h,
62.4-99.5% Br

Treatment of 5,13-di-tert-butyl-8,16-dimethyl [2.2]


R H2SO4 CF3SO3H
metacyclophane 7 with DBH (0.55 eq.) in CH2Cl2 at room
NO2 75% 87%
temperature led to the introduction of bromine on the bridged
CF3 81% 86% methylene group for the first time (Scheme 49) [79]. The
OMe 97% 97% reaction was accompanied by the formation of two by
CO2Me 71% 76% products 9 and 10. The yields of 9 and 10 depended on the
Scheme 46 amounts of DBH, so in the presence of 3.1 eq. of DBH only
compound 10 was obtained in 98% yield.

In 2005, Tsuboi and co-workers have found that DBH


H Br
(0.5-0.55 eq.) is able to act as an efficient reagent for
conversion of phenols and polyphenols to their corresponding
t-Bu Me t-Bu Me
ortho-monobromides in good to excellent yields (Scheme 47) DBH (0.55 eq)
[77]. CH2Cl2, r.t., 5 min

Me Bu-t Me Bu-t

COOMe COOMe
Br 7 8
DBH (0.5-0.55 eq)
CHCl3, r.t., 88-99%
R1O OH R1O OH t-Bu t-Bu

OR2 OR2
R1 = Bn, Me; R2 = Me, OH

Br Br
COOMe COOMe
Me Me Me Me
Br
DBH (0.5-0.55 eq) + Br Br
CHCl3, r.t., 80-99%
O OH O OH
1 O O t-Bu
R R1 t-Bu
R2 R1, R2 = H, Me, Ph R2
9 10
Scheme 49
Scheme 47
In 2006, Azarifar et al. reported an efficient method for
They also studied the regioselective bromination of

141
Application of N-Halo Reagents in Organic Synthesis

the conversion of various N-arylglycines to sydnones using Flourination reactions. Hiyana et al. reported the
DBH in the presence of NaNO2/Ac2O under mild and neutral oxidative desulfurization-fluorination of methyl xanthates with
conditions (Scheme 50) [80]. The following mechanism was (HF)9/pyridine and DBH (Scheme 53) [81]. Under the reaction
conditions, trifluoromethyl ethers (R-OCF3) were produced
through R-OCF2SMe intermediates.
Ar
DBH (0.8 eq) N
ArNHCH2CO2H N
NaNO2 (1.25 mmol)/Ac2O (1.5 mmol) O
O
0-5 C, CH2Cl2, 10-16 h, 80-94% S
R (HF)9/Py (2mL, 8.8 mmol of F-)
[R-OCF2SMe]
Scheme 50 O SMe
DBH (3 mmol), CH2Cl2
0 C, 1 h, 48-80%
proposed for these transformations (Scheme 51). R= Substituted Phenyl, Benzyl, n-C10H21 R-OCF3

Scheme 53
Br
O N O O N O
They also showed that -hydroxy orthothioesters 11
N + NaNO2 N Na + BrNO2 derived from both aromatic and aliphatic aldehydes were
Me Me
Me Br Br
Me successfully converted into their corresponding
difluoro(methyl thio)methyl ketones 12 using n-Bu4NH2F3 and
BrNO2 NO + BrO
DBH. Reactions were performed in CH2Cl2 at room
temperature (Scheme 54) [82].
+ NO
ArNH2CH2CO2H HOBr + ArN(NO)CH2CO2H
+ BrO
OH O
Ac2O + HOBr AcOBr SMe n-Bu4NH2F3 (5 mmol) SMe
R DBH (4 mmol)
SMe R F
SMe CH2Cl2, 10 min, r.t.
28-95% F
AcOBr
Ar H 11
O 12
N R= Aryl or Alkyl
Ar OAc
N OH N
-AcOH O OH
+ BrO Scheme 54
N
O

Ar H Ar H Correspondingly, when orthothioesters were selected as


N N
OAc BrO
+ HOAc + HOBr
the substrate the monobromo- difluorinated compounds were
N N + O
O OH O obtained as the main products (Scheme 55) [83]. A

Scheme 51
Br
SMe n-Bu4NH2F3 (3 mmol) SMe
They also showed that DBH is able to promote the R DBH (3 mmol) R
SMe F
bromination of sydnones to their 4-bromo-substituted SMe CH2Cl2, 20 min, 0 C to r.t.
F
52-87%
congeners in excellent yields in DMF at room temperature
Scheme 55
(Scheme 52).

Ar H Ar Br
N
DBH (2 mmol) N mechanism which initiated by the electrophilic attack of Br+ at
N + N +
O
O DMF, r.t., 2.0-2.6 h
O
O the sulfur atom of the substrate has been suggested (Scheme
94-99%
56).
Scheme 52

142
Kolvari et al.

treatment with n-Bu4NH2F3/DBH, were efficiently converted


SMe
Br+
SMe SMe to -fluorosulfides (Scheme 58) [84,85]. The formation of the
R R F R
SMe SMe SMe
SMe SMe -MeSBr F
Br H R1 n-Bu4NH2F3 (1.4-3.5 mmol) F R1
F DBH (1.4-2.5 mmol) RS-C
RS-C 2
H Br
H R CH2Cl2, 10 min R2
Br H SMe Br r.t., 33-90%
-MeSBr
SMe
R R
SMe -HF F R1= Substituted Phenyl, Alkyl
F F R2, R3= H, CF2SMe, Aryl, Alkyl,
F

H Br Scheme 58
H Br
SMe
SMe R F
R
F product can be rationalized by the following mechanism
F
F
(Scheme 59). On the basis of the proposed mechanism,
electrophilic attack of Br+ to organic sulfide produces a
Scheme 56 sulfonium ion 14, which is attacked by the fluoride ion to give
the final product. The reaction of RCH(SMe)CF2SMe, under

They also found that when RCH(OAc)C(SMe)3 was used


H R1 H R1 R1
instead of RCH2C(SMe)3, the corresponding difluoro acetate Br+ + -HBr +
RS-C RS-C 2 RS=C 2
was obtained as the main product (Scheme 57) . R2 R R
Br
13 14
F R1
H OAc H OAc F
SMe n-Bu4NH2F3 (5.2 mmol) F RS-C 2
R DBH (4.4 mmol) R R
SMe F
SMe CH2Cl2, 10 min, 0 C, SMe Scheme 59
Argon atmosphere
53-70%
R = 1-Naphtyl, 2- Naphtyl, n-C11H23 the same conditions, ended up with the formation of
Scheme 57 trifluorosulfides, [RCF(SMe)CF2SMe], as the main products
(Scheme 60).
Furuta et al. reported that various organic sulfides, on Shimizu et al. reported an efficient method for the

H SMe F SMe
n-Bu4NH2F3 (3.5 mmol)
CF2SMe DBH (2.5 mmol) CF2SMe
CH2Cl2, r.t., 20 min
68%

Scheme 60

S S HFP-DA (4.0 eq) F F


DBH (2.0 eq)
H2O (4.0 eq), CH2Cl2
-78 to -20 C, 80 %

Scheme 61

143
Application of N-Halo Reagents in Organic Synthesis

conversion of gem-disulfides to the corresponding gem- They have also reported a mild method for the preparation
difluorinated compounds by a combination of of trifluoromethyl ethers (R-OCF3). The reaction was carried
hexafluoropropene-dimethylamine and DBH (Scheme 61) out by the reaction of dithiocarbonates (R-OCS2Me) with a
[86]. reagent system consisting of 70% HF/Pyridine and DBH
Using this method, 1,3-dithiolanes derived from ketones (Scheme 65) [88]. When the reaction was applied to
gave better results than those from aldehydes. The probable ROCS2Me wherein R = secondary alkyl, tertiary alkyl or
mechanism of the reaction is shown in Scheme 62. benzylic group, fluorination was leading to corresponding
alkyl fluorides (R-F) (Scheme 66).

BrS S 70% HF/Py (40 mmol)


BrS
F DBH (3 mmol)
S SBr PhCH2CH2CH2-O-C-SMe PhCH2CH2CH2-O-CF3
S BrF S S
S F CH2Cl2, -78 Cto 0 C, 1 h
75%

BrS
Scheme 65
Br
BrF S F F F F

70% HF/Py (40 mmol)


Ph DBH (3 mmol) Ph
Scheme 62
CH2Cl2, -78 C to 0 C, 1 h F
OCS2Me 94%
Furuta et al. have found that when methyl
arenecarbodithioates and ,-unsaturated carbodithioates were Scheme 66
treated with n-Bu4NH2F3 in the presence of DBH,
trifluoromethyl and 3,3,3-trifluoropropenyl substituted Due to their stability and stereoselectivity on the glycoside
aromatic compounds were obtained in acceptable yields synthesis, the glycosyl fluorides have recently received
(Schemes 63 and 64) [87]. considerable attention [89]. Among different methods reported
for the preparation of glycosyl fluorides, bromofluorination of
glycals with SiF4/DBH/H2O reagent system in 1,4-dioxane in
CS2Me CF3 the presence of HMPA was considered as one of the most
n-Bu4NH2F3 (5.0 mmol) useful and stereoselective methods for the preparation of
DBH (4 mmol)
CH2Cl2, 63% bromofluoro sugars [90] (Scheme 67). Stereoselectivity of the
reaction is strongly influenced by the solvent polarity. In the
Scheme 63

CS2Me n-Bu4NH2F3 (5.0 mmol) CF3


DBH (4 mmol)
CH2Ph CH2Cl2, 0.5 h, 43% CH2Ph

Scheme 64

OR
OR OR
OR
RO SiF4(gas), DBH (1.1 mmol) Br
RO O H2O (1.0 mmol), HMPA (0-5 mmol) RO RO
RO O RO O RO
+ + RO O
1,4-dioxane (4 mmol) F
0 or 50 C, 1h Br
F F Br

R= Benzyl and Acetyl


Scheme 67

144
Kolvari et al.

absence of HMPA, formation of the -fluorides predominated DBH has also been used for the efficient oxidation of
with ratio of 74:26, and the addition of HMPA improved the mono and bis-urazoles to their corresponding triazolinediones
selectivity in favor of the -isomers. The best stereoselectivity both in solution and under solvent-free conditions (Scheme
was obtained when the reaction was carried out in the presence 71) [94].
of 3.0 eq. of HMPA, in which the - vs. -isomer ratio was
92:8.
H O O H O O
Hiyama et al. has also reported that when alkene was N N
N N
A or B
treated with KHF2/HF/n-Bu4NF/DBH reagent system, the N R2 N N R2 N
related bromofluorinated product was obtained in good to high N N N N
R1 O O R1 O O
yields (Scheme 68) [91]. The stereochemistry of the addition
of F and Br was anti for all of the olefins. A: DBH (2 mmol), 4h, 99-100%, CH2Cl2, r.t.
B: DBH (2 mmol), 4h, 33%, Solvent-free, r.t.
O F O R1 = H, Na, R2 = -(CH2)6- , -C6H4-CH2-C6H4-
n-Bu4NH2F3 (1.5 mmol)
DBH (1.5 mmol) Br
OMe OMe
CH2Cl2, r.t., 13 h, 85 % Scheme 71

Scheme 68 Khazaei et al. reported a simple method for the oxidation


of thiols to disulfides by the use of DBH in dichloromethane
Oxidation Reactions (Scheme 72) [95]. An inconceivable decrease in the reaction
In 2004, oxidation of 1,3,5-trisubstituted pyrazolines to the time was observed in the absence of solvent.
corresponding pyrazoles using DBH under both heterogeneous
and solvent-free conditions was reported by Azarifar et al.
(Scheme 69) [92]. DBH (1-1.5 mmol)
2 RSH RSSR
Solid phase (1-10 min, 87-91%)
CH2Cl2 (0.8-4 h)
R1 N 2 R1 N
N R
2
A or B N R R = Aryl or Alkyl

R3 R3 Scheme 72
A: DBH (1-4.25 mmol), 0.3-1.75 h, 70-98%, CCl4, r.t.
B: DBH (2-18 mmol), 0.3-4.5 h, 63-92%, Solvent-free, r.t.
A mechanism was proposed for this reaction (Scheme 73).
R1 = Ph, Acetyl, R2 = Aryl, R3 = Substituted Phenyl

Scheme 69 O
Br O
N
The same group has also shown that when the reaction was 2RSH + N Br 2 R S Br N
N
carried out in the presence of silica gel under microwave H
O
irradiation, the products were obtained during very short II O
I
reaction times (Scheme 70) [93].
O
DBH (2.5-4 mmol) H
R1 N R1 N N
N Ph Silica gel (20-32 mg)
N Ph 2 RSBr + N H
II
MW, 1-5 min, 74-90%
R2 R2 O
III
R1 = Aryl, R2 =Substituted Phenyl
2 RSBr RSSR + Br2

Scheme 70
Scheme 73

145
Application of N-Halo Reagents in Organic Synthesis

The same subject has also been investigated by another DBH (1.2 mmol)
R1 N N R3 R1 N N R3
group in 2005 [96]. DBH in accompanying with NaNO2 was 1-15 min, 63-89%
R2 H
used as a co-catalyst for the acceleration of the aerobic R2 Br
1
R = Substituted Benzyl and Phenyl,
oxidation of benzylic alcohols in water catalyzed by TEMPO R2 = H, Substituted Phenyl,Methyl, R3= Substituted Benzyl
(Scheme 74) [97]. All reactions were performed at 80 C and
the products were obtained in good to high yields. Scheme 76

R1 TEMPO (0.1 mmol)


R1 relatively pure products and high yields. Since the rate of the
DBH ( 0.4 mmol)
OH O reaction did not change in the presence of a radical initiator
NaNO2 (0.4 mmol)
R2 H2O (3 ml), oil bath (80 C), R2 (benzoyl peroxide) or a radical inhibitor (butylated hydroxy
1.5-6 h, 88-98%
R1, R2 = Alkyl and Aryl
toluene, BHT), an ionic mechanism, which involved
bromination of imidazolidine`s nitrogen, followed by
Scheme 74
deprotonation and displacement of a bromide ion, was
proposed for the reaction (Scheme 77).
Recently, Rievera et al. reported a suitable method for the
synthesis of 5-substituted-2-amino-1,3,4-oxadiazoles, as
Miscellaneous Reactions
biologically active important molecules, via oxidative
Walters et al. studied the use of DBH for the oxidation of
cyclization of thiosemicarbazides using DBH in the presence
hydroxylamines to gem-halonitro compounds in the presence
of potassium iodide (Scheme 75) [98]. The main advantage of
of ozone (Scheme 78) [100]. The bromo derivatives were
this method is its applicability for the large scale synthesis of
obtained in 44-73% yields.
the hydroxyl oxadiazoles.
In 2006, Salerno et al. have used DBH as an efficient
dehydrogenating agent for the oxidation of N,N-dibenzyl- and NO2
DBH (3 mmol), O3
N-aryl-N-benzyl-imidazolidines to their 4,5-dihydro-1H- N OH
EtOAc/NaHCO3(aq)
Br
imidazolium salts (Scheme 76) [99]. The main advantages of
the selected method are: low reaction times, obtaining
Scheme 78

O KI (1.54 mmol)/ H2O (2mL) O


H DBH (3.85 mmol)/CH3CN (10 mL) Ar NH2
N NH2
Ar N i-PrOH (8 mL) N N
H
S NaOH (5N, 1.54 mL)
1h, 10 C, 53-97%

Scheme 75

O O
Br
Br
Br N
N R1 N N R3 N
N Br 1 3 +
R N N R
+ R2 H
R2 H O
O
O
H
R1 N N R3 + N
N H

R2 Br
O

Scheme 77

146
Kolvari et al.

F F
When 1,3-dithiolanes bearing a phenyl or substituted
aromatic group and a methyl (or methylene) group attached to Me
Me
MeO O MeO
C-2 were treated with DBH in the presence of HF/pyridine, a O
Me
Me DBH
rearrangement took place instead of gem-difluorination HF/Pyridine
(Scheme 79) [101]. A mechanism was proposed for this S S Me
MeO O
rearrangement, which is shown in Scheme 80. Me
DBH was also applied for the synthesis of S
diglicodeoxynucleotides containing 2-O-(trifluoromethyl) S
adenosine in the presence of HF/pyridine (Scheme 81) [102]. Scheme 79
Using this method, products were obtained in relatively
acceptable yields under mild reaction conditions. glycosyl S,S-acetals to their corresponding O,O-acetals using
Madhusudan et al. reported the facile conversion of DBH under mild and neutral conditions (Scheme 82) [103].

S S S S Br S S Br
H
Me Br Me Me - H+
MeO O MeO O MeO O
Me Me Me

S S
S S Br H S
S
H
Me - H+ Me
Me
MeO O MeO O
MeO O Me Me
Me

Scheme 80

NH2 NH2 NH2


N N N
N N N
N N N N
N N
HF/Py (5 mL)
O O DBH (3.75 mmol) HO HO
O O
TIPDS -78 C - 0 C, CH2Cl2 +
O OH OH OCF3 O O
F F
TIPDS = tetraisopropyldisiloxane-1,3-diyl

Scheme 81

OAc OAc
CH(SEt)2 DBH (1 mmol) CH(OMe)2
AcO AcO
30 min, 86%,
OAc OAc r.t. OAc OAc

Scheme 82

147
Application of N-Halo Reagents in Organic Synthesis

The proposed mechanism of this reaction is illustrated in under the same conditions, glycofuranosides were obtained in
(Scheme 83). When glyclic glycosyl S,S-acetals were reacted good to high yields (Scheme 84). In the case of

Br Br
H SEt
OAc H SEt H H SEt
OAc OAc OAc
OAc H SEt
OAc H SEt -EtSBr OAc H SEt Br OAc H OMe
DBH
H OAc
H OAc H OAc H OAc
MeOH

OAc
OAc OAc OAc
AcO
AcO AcO AcO

H H OMe
OAc OAc
-EtSBr OAc H OMe MeOH OAc H OMe

H OAc H OAc

OAc OAc

AcO AcO

Scheme 83

OH
AcO O
CH(SEt)2 DBH (1 mmol) OAc OMe
HO 30 min, 86%,
OH OH r.t.
OAc
Scheme 84

Br
H SEt
OH H SEt H
OH H
OH H SEt OH O
DMF OH H SEt OH H SEt OH H SEt
H OH
H OH H OH H OH

OH
OH OH OH
HO
HO HO HO

H H H
O O O
OH H SEt OH OH H OR
H ROH
Br
H OH H OH H OH

OH OH OH
HO HO HO

Scheme 85

148
Kolvari et al.

glycofuranoside formation, the authors proposed that product Recently, DBH/NaNO2/wet SiO2 has been used as an
was formed by intramolecular nucleophilic attack from the efficient reagent system for the direct nitration of phenols
hydroxyl group at C-4 following by a nuclophilic attack of the (Scheme 87) [106]. All reactions were performed at room
alcohol at C-1 (Scheme 85). temperature and under completely heterogeneous conditions.
Because of the unstability of -aminoaldehydes, which are
reckoned as extremely valuable chiral building blocks in
OH OH
asymmetric synthesis [104], the preparation of N-protected
DBH (1mmol) NO2
derivatives of these compounds is attracted the attention of NaNO2 (1mmol)
many organic chemists. Davis et al. reported that the wet SiO2(50% w/w, 0.4 g)
30 min, 90%
hydrolysis of sulfimine derived N-sulfinyl--amino-1,3- Cl Cl
dithianes with aqueous DBH affords the corresponding N- Scheme 87
tosyl--aminoaldehydes in good yields and high enantiomeric
purities (Scheme 86) [105].
The reaction did not proceed in the absence of wet SiO2. The
following mechanism was proposed for the description of the
O
S
reaction pathway (Scheme 88).
Tosyl
p-Tolyl NH 1) DBH (2 eq.) NH
2) Na2SO3
In the same manner, when N,N-dialkylamines were treated
H H
R S R with DBH/NaNO2/wet SiO2 reagent system, their
S O corresponding N-nitrosated derivatives were obtained in good
to excellent yields (Scheme 89) [107]. The reaction conditions
R = Ph, i-Pr, t-Bu
are very mild and completely heterogeneous.
Scheme 86

O O
Br H
N N
N Br N H
+ 2H2O (wet SiO2) + 2HOBr

O O
HOBr + NO2 HNO2

HNO2 + 2H NO + H3O

2HNO2 N2O3 + H2O

N2O3 NO + NO2

2NO2 N2O4

2NO O2 + N2O2 N2O4

OH OH O OH
NO2
+ NO +H NO2

-NO
-H
Cl Cl Cl Cl

Scheme 88

149
Application of N-Halo Reagents in Organic Synthesis

DBH (0.6 mmol)


ethers with 3,4-dihydro-2H-pyran in the presence of DBH.
NaNO2 (2 mmol)
O NH O N NO The method is mild and the products were obtained in high
wet SiO2 (50% w/w, 0.4g)
yields (Scheme 92). The method was also used for the
7 min, 75%

Scheme 89
A or B
ROH ROY
Recently, an efficient and high yielding method for the
acylation of alcohols with acetic anhydride using DBH has A: DBH (0.015 mmol), HMDS (7.0 mmol), CH3CN, r.t.,
immediately-15 min, 80-95%
been reported (Scheme 90) [108]. The proposed mechanism, B: DBH (0.5 mmol), DHP (1.4 mmol), n-Hexane, r.t.,

Y: TMS, THP
R= Aryl or Alkyl ( 21 substrates)
OH DBH (0.05 mmol)
OAc
Ac2O (2mmol) Scheme 92
R1 R2 1
R R2
CH2Cl2, r.t., 1-38 h,
80-95%
R1, R2 = Alkyl or Aryl selective trimethylsilylation or tetra-hydropyranylation of
various types of alcohols in the presence of tertiary alcohols
Scheme 90 (Scheme 93). The mechanism which has been reported for the
above mentioned method is the same as that reported for the
tetrahydropyranylation of alcohols in the presence of TCCA
which was based on activation of Ac2O by the in situ (Scheme 28).
generated H+, is shown in Scheme 91. DBH has been found to efficiently catalyze the conversion
DBH efficiently enhanced the rate of trimethylsilylation of of various 3-arylsydnones to their corresponding 4-acetyl
different types of alcohols with HMDS [109]. Alcohols were derivatives in the presence of acetic anhydride under neutral
also converted to their corresponding tetrahydropyranyl conditions in satisfactory yields (Scheme 94) [110].

O
O O O
Br
N Br
+ Ac2O N + O

O O O
H
+ ROH ROAc + N
N

O O O
O
H Br +
N + Br N OH
O

Scheme 91

DHP, DBH
n-Hexane
Me3COH + OH OTHP + Me3COTHP
r.t., 30 min

95% 0%

Scheme 93
150
Kolvari et al.

O
Ar
1-BROMO-5,5-DIETHYLBARBITURIC ACID
N Ar
DBH, AcO2 N AND 1,3-DIBROMO-5,5-DIETHYLBARBI-
N N
O
O Reflux
O
O TURIC ACID
Scheme 94 1-Bromo-5,5-diethylbarbituric acid 16 and its 1,3-dibromo
analogue 17 were prepared in 1991 but found little attention of
1,3-DICHLORO-5,5-DIMETHYLHYDANTOIN organic chemsits [115]. They have been used for the oxidative

Contrary to DBH, its chlorinated analogue, 1,3-dichloro-


5,5-dimethylhydantoin (DCH, 15), has found very limited O O O O
applications and only few reports are available on its uses in
N N N N
Br Br
organic synthesis. These reports are included -chlorination of H Br
acetophenones (Scheme 95) [111], oxidative cleavage of O O

oximes [112,113] and oxidation of urazoles [114]. 16 17

O
cleavage of different kinds of trimethylsilyl ethers in good
Cl N
N yields at room temperature (Scheme 96) [116]. The conversion
Cl
of benzyl trimethylsilyl ether to benzaldehyde in the presence
O
of both 16 and 17 was conducted in different solvents. The
15
results showed that the efficiency and the yield of the reaction

O O
O O
Cl H
N N
p-TsOH +
R + 1/2 R 1/2 N
N CH3OH/30-35 C Cl O
O H
Cl
R = H, p-CH3, p-OCH3, p-Cl, p-NO2, p-Br, m-NO2, o-NO2

Scheme 95

OSi(Me)3 O
A or B
CH2Cl2

A : 16(1.4 eq), r.t., 3-15 h, 80-90%


B : 17 (0.7 eq), r.t., 0.5-9 h, 81-95%

Scheme 96

OH
OH
HO OH
17 (Cat., 20% eq) / HMDS (1.5 eq) TMSO OTMS
r.t./ neat/ 85%
Br
Br
Scheme 97

151
Application of N-Halo Reagents in Organic Synthesis

X
in dichloromethane was better than in other solvents. THP-
Cl
ethers remained intact under the reaction conditions.
Silylation of alcohols and polyols is one of the most N
O N
commonly used methods for their protection. H H
Cl
Cl Cl
Trimethylsilylation is a classic way to produce volatile R1 C R or R1 C H R1 C R or R1 C Cl
Base or Acid
derivatives of alcohols and polyols. The application of 17 as a R2 R2 R2 R2

catalyst was described in the protection of different alcohols


Acid = HNO3, H2SO4, H3PO4, p-TsOH, HCl, ZnCl2, CuCl2, FeCl3, AlCl3,
by HMDS in good to high yields in the absence of solvent at Base = NaH
X = Cl or OMe
room temperature. A good selectivity was observed for the
protection of alcohols over phenols (Scheme 97) [117]. Scheme 98

2,4,5-TRICHLORO- AND 2,4-DICHLORO-5- synthesis. They can be applied as halogenating agent or as


METHOXYPYRIDAZIN-3(2H)-ONE catalyst in organic transformations. The application of some
N-halo sulfonamides such as N,N-dihalo sulfonamides was
2,4,5-Trichloro- and 2,4-dichloro-5-methoxypyridazin- reviewed by Koval [119,120]. Herein, application of a broad
3(2H)-one were synthesised by Park et al. as two novel range of N-halo sulfonamides is reviewed.
reagents in 2005 [118]. -Chlorination of active
methylene/methine compounds with these reagents in the Halogenation Reactions
presence of either Lewis or protic acids in dichloromethane Khazaei et al. have reported a novel compound that was
(for Lewis acid) or water (for protic acid) at room temperature synthesized via bromination of methyl methacrylate with high
gave also -monochlorides and/or ,-dichlorides selectively yield. This brominated compound is suitable for
in good to excellent yields (Scheme 98). polymerization as an adhesive (Scheme 99) [121].
Carbanionic substrates were subjected to chlorination with
N-HALO SULFONAMIDES poly[4-vinyl-N,N-dichlorobenzenesulfonamide]. Chlorinated
products were obtained in good yield and short reaction time
N-halo sulfonamides have been widely used in organic under mild condition (Scheme 100) [122].

CH3
CH3 CO2Me
CO2Me CCl4
CH2 C +
CH2 C + 10 h, 87% H3C SO2NCH2
H3C CH2Br
CH3 SO2NCH2
2 H
Br

CH3 CH2Br
CO2Me CO2Me H2
heat
CH2 C + CH2 C C C C C
CH3 CH2Br H2

CH3 MeO O O OMe CH3


O H H O
H2 H2
S N C C N S
O O

CH3 CH3

Scheme 99

152
Kolvari et al.

p + 2R- THF 2RCl p


NCl2 + NH2 range of organic compounds (Scheme 101) [123-132].
40 - 95%
40 -270 min Bromination of allylic compounds was described by using
N,N'-dibromo-N,N'-ethanediylbis(2,5-dimethylbenzene)sulfon-
p NCl2 (CH-CH2) amide (Scheme 102) [134].
n
Regioselective bromination of activated aromatic
compounds was carried out with N,N'-dibromo-N,N'-
ethanediyl bis(p-toluenesulfonamide) (BNBTS) [128].
SO2NCl2
Ghorbani and Jalili reported the preparation of N,N'-
Scheme 100 tetrabromobenzene-1,3-disulfonamide (TBBDA) and poly N-
bromobenzene-1,3-sulfonamide (PBBS). These new reagents
Recently some new N-halo sulfonamides have been
have been used for bromination of activated aromatic
reported as chemoselective brominating agents for a broad
compounds in good yields (Scheme 103) [129].

CH3
H3C

SO2NCH2 )
2
Br SO2NBr2 SO2NCl2
I II III

H3C SO2
Br2N NBr2
N Br SO2NCH2 ) S S
2
H3C SO2 Br O O O O

IV V VI

H 3C
Br Br
( H2C N N
S S CH2) n
SO2NCH2 )
O O O O 2
I
VII VIII

I : N,N'-dibromo-N,N'-ethanediylbis (p-toluenesulfonamide) [BNBTS]


II : N,N-dibromo(p-toluenesulfonamide)
III :N,N-dibromobenzenesulfonamide
IV :N-bromobis(p-toluenesulfonyl)amine [NBBTA]
V : N,N'-dibromo-N,N'-ethanediylbisbenzenesulfonamide
VI : N,N'-tetrabromobenzene-1,3-disulfonamide [TBBDA]
VII :poly N-bromo benzene-1,3-sulfonamide [PBBS]
VIII: N,N'-diiodo-N,N'-ethanediylbis(p-toluenesulfonamide) [NIBTS]

Scheme 101

CH3 CH3
CCl4
+ Alkene Bromoalkene +
H3C (PhCO2)2 H3C
SO2NCH2 ) SO2NCH2 )
2 2
Br H

Scheme 102

153
Application of N-Halo Reagents in Organic Synthesis

R R
and characterization of carbonyl compounds. To achieve this
PBBS or TBBDA aim N-halo compounds have been used widely as versatile
CH2Cl2 reagents. Recently a broad range of N-halosulfonamides
25-40 C (NHSs) has been reported for regeneration of carbonyl
30-180 min Br
79-98% compounds from oximes (Scheme 105) [130,131,135-139].
R= -NHCOCH3, -OCH3, -NEt2 N,N-Dibromo-N,N-1,2-ethanediyl bis(p-toluenesulfon-
amide) (BNBTS) has catalytically been applied for
Scheme 103
tetrahydropyranylation of a various range of alcohols and
phenols in dichloromethane and tetrahydropyranylation of
these compounds has been also carried out in methanol at
N,N'-Diiodo-N,N'-ethanediylbis(p-toluenesulfonamide)
room temperature (Scheme 106) [140].
(BNITS) as a novel iodinating agent has been used for
iodination of some aromatic compounds in high yields
(Scheme 104) [132].
BNBTS, CH2Cl2, r.t.
ROH +
O BNBTS, MeOH, r.t.
O O
R R R= 1, 2, 3, Alkyl and Aryl R

2 Cat. TFAA + BNHTS


+ BNITS 2
CH3CN, 81 C Scheme 106
3-5 h, 90-93%
I
Scheme 104 Conversion of 1,1-diacetates to aldehydes has been
described using BNBTS in high yield and short time at room
temperature under solvent-free condition (Scheme 107) [141].
Cleavage and Formation of Carbon-Hetroatom Deprotection of 2,4-dinitrophenylhydrazones to their
Bonds corresponding carbonyl compounds have been reported in
The protection of carbonyl compounds is very important in good yields with BNBTS under microwave irradiation
multistep synthesis. Protected carbonyl compounds such as (Scheme 108) [142].
oximes, semicarbazones, phenylhydrazone derivatives, BNBTS has been used for deprotection of aliphatic and
diacetals, dithianes and etc. are easily prepared and are highly aromatic 1,3-dithianes to their corresponding carbonyl
stable compounds used extensively for protection, purification compounds under mild condition (Scheme 109) [143].

NOH NHS O
1 2 1
R R R R2

R1, R2 = Aryl and Alky

O Br
O H3C (CH-CH2)
S N Br n
NHS : O O S N
O Br SO2NCH2 )
2
Br
SO2NCl2

Scheme 105

154
Kolvari et al.

OAc O
solid state, H2O, r.t. + BNHTS + 2AcOBr
+ BNBTS H
R OAc R
1.5 to 4 min
90-98%

R = Alky or Aryl

Scheme 107

R1 R1 TBBDA or PBBS
BNBTS HMDS
N NH NO2 O RXH RXSiMe3
CH2Cl2, MW CH2Cl2 or solvent free, r.t.
R2 R2
30-60 min
O2N
89 -95% X = S or O
R1, R2 = Alky or Aryl R= Aryl, Alkyl

Scheme 108 Scheme 111

n
O Oxidation Reactions
BNBTS, AgNO3
S S Another important application of N-halo reagents in
80% aq. CH3CN, r.t. R1 R2
80-90% organic chemistry is the oxidation of different functional
R1 R2
15-30 min groups through the release of halonium ions. TBBDA and
R1, R2 = Alkyl, Ary, H TCM were used as effective oxidizing agent for the
n = 1, 2 conversion of urazoles and bis-urazoles to the corresponding
Scheme 109 triazolinediones under mild and heterogenous condition at
room temperature with good to excellent yields (Scheme 112)
Deprotection of 1,3-oxathiolanes to carbonyl compounds [146].
has been carried out with BNBTS in good yields under mild
Cl
conditions (Scheme 110) [144]. HN
Br2N NBr2 N Cl
S S N NH
n O O O O O N
BNBTS Cl NH
O S
80% aq. CH3CN, r.t. R1 R2
R1 R2 0.5-10 h N,N'-tetrabromobenzene-1,3- Trichloromelamine (TCM)
82-93% disulfonamide (TBBDA)
n=1, 2 R1 H
R1, R2 = H, Arly or Alkyl N N TCM or TBBDA N N
CH2Cl2, r.t. O O
O N O N
1.5-22 h
Scheme 110 R2 R2

R1 = Na, H, R2= Alkyl or Aryl


Poly(N-bromobenzene-1,3-disulfonamide) (PBBS) and
N,N,N',N'-tetrabromobenzene-1,3-disulfonamide (TBBDA) Scheme 112
were reported as efficient catalysts for the silylation of
alcohols, phenols, and thiols in the presence of HMDS under
various conditions (Scheme 111) [145]. Since there are few Efficient oxidative coupling of thiols has been made by
reports on the silylation of thiols in the literature, the method BNBTS for production of the corresponding disulfides at room
is suitable and practical for this purpose. temperature with good to excellent yields (Scheme 113) [147].

155
Application of N-Halo Reagents in Organic Synthesis

BNBTS OH OCOCH3
R-SH RS-SR
CH2Cl2, r.t. Ac2O, Catalysts
1.5-3.8 h 90-95% R1 R2 R1 R2
CH2Cl2, r.t., 1-48 h
R = Alkyl or Aryl 90-98 %

Scheme 113 R1, R2 = H, Alkyl or Aryl


CH3

N,N,N',N'-tetrabromobenzene-1,3-disulfonamide (TBBDA),
Catalysts: X= Br or Cl
BNBTS and PBBS were used as efficient reagents for the
oxidation of 1,3,5-trisubstituted pyrazolines to their SO2NX2
corresponding pyrazoles in solvent-free conditions both under
Scheme 116
microwave irradiation or at room temperature (Scheme 114)
[148-151].
A combination of equal amount of Ph3P and BNBTS has
been used for the conversion of carboxylic acids into esters
and amides in the presence of alcohols and amines,
R1 R2 R1 R2
BNBTS or TBBDA respectively (Scheme 117) [155]. Authors have suggested that
N N N N
MW, Solvent-Free
Ph or CCl4, r.t. Ph
or Solid Phase, r.t.
R1, R2 = Aryl 1) BNBTS, Ph3P 1) BNBTS, Ph3P
CH2Cl2, 0 C CH2Cl2, 0 C
R2R3NCOR RCO2H RCO2R1
Scheme114 2) or R2R3NH, Py, r.t. 2) R1OH, Py, r.t.

R= H, Aryl or Alkyl; R1= Alkyl or Aryl; R2, R3= H, Alkyl or Aryl


Py : Pyridine
Poly(p-N-chlorostyrenesulphonamide) was used as an Scheme 117
efficient polymeric oxidizing reagent for oxidation of primary
and secondary alcohols to corresponding carbonyl compounds the reaction is initiated via nucleophilic attack of
in the presence of DMSO in reasonable yields (Scheme 115) triphenylphosphine to N-bromosulfonamide, followed by
[152]. nucleophilic attack of alcohol or amine that afforded the
corresponding esters or amides (Scheme 118).
O Cl
OH P S N O
CH3 CH3
O
R1 R2 R 1
R2
CH2Cl2
0 C
31-95 %
CH2Cl2
R1, R2= H, Alkyl or Aryl 2Ph3P + SO2NCH2 SO2NCH2
2 2
Br Ph3PBr
Scheme 115 RCO2H - Sulfonamide

R1OH R2R3NH2
Miscellaneous Reactions
N-halo reagents have been also applied as catalyst in
[Ph3P-OCOR]Br
esterification reactions. N,N-dibromo(p-toluenesulfonamide)
and N,N-dichloro(p-toluenesulfonamide) catalyze acetylation
RCO2R1 R2R3NCOR
of structurally drivers alcohols by the reaction of acetic Reaction intermediate
anhydride in chloroform at room temperature (Scheme 116)
[153-154]. Scheme 118

156
Kolvari et al.

Me Me
O I O H
N Na2CO3 N
2R + S CH2 2 S CH2
H O 2 R OMe + O 2
O MeOH, dark O
2.5-42 h
65-90%
R = Alky or Aryl
Scheme 119

N,N-Diiodo-N,N-1,2-ethanediylbis(p-toluensulfonamide) sulfonamide (2-NsNCl2) as a nitrogen source in acetonitrile.


(BNIBTS) has converted aldehydes to methyl esters in the The corresponding diamine derivatives were stereoselectively
presence of methanol in good yields at room temperature obtained with good yields (Scheme 122) [159].
(Scheme 119) [156].
NHAc
N-Bromosulfonamides 18 and 19 reacted with several
COOR 1) 2-NsNCl2/MeCN COOR
types of arenes in the presence of KSCN at 0 or 25 C to Ar Ar
2) Na2SO3(aq)
afford aryl thiocyanates (Scheme 120) [157]. NHNs-2
61-74%

SCN R = Me or Et

18 or 19
KSCN Scheme 122
0 or 25 C
R 2-4 h
70-98% R

CHLORAMINE T
CH3 CH3

Sodium N-chloro-p-toluenesulfonamide, Chloramine T 20,


has diverse chemical properties. It is a commercially available,
SO2 N Br SO2 N CH2
2 inexpensive, water-tolerant, non-toxic and easy to handle
CH3 Br CH3 Br
chemical. Chloramine T acts both as a source of halonium
18 19
ion as well as a nitrogen anion. As a result, it reacts with a
Scheme 120
wide range of functional groups, leading to an array of
molecular transformations. Chloramine T has been used in
A variety of olefins have been reacted with N-chloro-N-
various types of chemical transformations such as
sodium-2-nitrobenzenesulfonamide (o-NsNClNa) in the
aminohydroxylation, aminochalcogenation of alkenes, allylic
presence of catalytic amounts of copper triflate to give vicinal
aminations, and aziridinations [160].
halo amines stereoselectively (Scheme 121) [158].

CH3
Cl
1) o-NsNClNa
COOR CuOTf (10 mol %) COOR
Ar Ar
2) Na2SO3(aq)
NH(o-Ns)
63-76% SO2NClNa
R = Me, Et or i-Pr
20
Scheme 121

Tandem diamination of cynamic esters have been Wang and Li carried out oxidation of hydrocarbons to their
successfully carried out with N,N-di-chloro-2-nitrobenzene- corresponding ketones using the Fe(TPP)Cl/Chloramin T/O2

157
Application of N-Halo Reagents in Organic Synthesis

system (Scheme 123) [161]. Chloroamine T reacted with a variety of 1,3-dioxathiolanes


and 1,3-dithiolanes and cleaved them to the original carbonyl
NHTs
compounds (Scheme 126) [165].

not found S
Chloramine T Chloramine T
O CHO
Fe(TPP)Cl MeOH, H2O
CH3CN S
24h
83 % Scheme 126

Aziridine, an important three-membered heterocyclic ring


system, is a useful precursor for the synthesis of several
NH N biologically important compounds such as amino acids, amino
TPP: sugars and alkaloids. For this purpose Chloramine T has been
N HN
used in the presence of various catalysts (Scheme 127) [166-
172].

Scheme 123 R1 R3
Ts
Chloramine T, Cat. R1 N R3
Solvent or
Chloramine T was used for the conversion of some amines R2 R4 solvent-free, r.t. R2 R4
and imidazoles to corresponding oxidized compounds under
Solvent: CH3CN or H2O
catalytic conditions (Scheme 124) [162,163]. Catalyst:HPA/CTAB/MS 5 A, Py/HBr3, I2/BTEAC, CuI/Ptc, MPHT or NBS
R1, R2, R3, R4 = Alkyl or Aryl
MPHT = N-methylpyrrolidine-2-one hydrotribromide

N NH2
Chloramine T Scheme 127
Ru Complex
N H3O+ NH2
H

CH2CH2NH2 CH2COOH Although mechanistic aspects of the aziridination have not


Chloramine T been yet cleared, Sudalai et al. have suggested an interesting
Ru Complex mechanism for aziridination in the presence of NBS as catalyst
H3O+
(Scheme 128) [167].
Scheme 124

TsNClNa + NBS
Synthesis of chlorolactones by reaction of unsaturated
carboxylic acids with Chloroamine T has been reported TsNClNa

(Scheme 125) [164]. Ts TsNBrCl + NaX


N R R'
Cl-Br O
ClH2C
R R' Br X= Cl or N
OH H Br
-
Benzene, CH3CO2H + Ts-N
+ Ts N Na O R H Cl O
R R'
O Ts-N R'
Cl Cl
O

Scheme 125 Scheme 128

158
Kolvari et al.

2-Pyrazoline and 2-isoxazolines have been prepared by the (Scheme 130) [174]. Minakata et al. reported a new synthetic
reaction of araldehyde hydrazones and aldoximes with procedure for the amino chlorination of a variety of olefins
bifunctional olefins in the presence of Chloramine T. The and conjugated dienes to obtain vicinal chloramine derivatives
generated 2-pyrazolines were also oxidized to the with a combination of Chloramine T and carbon dioxide
corresponding pyrazoles in the course of the reaction (Scheme (Scheme 131) [175].
129) [173].
Reaction of araldoximes with 4 eq. of Chloramine T in
refluxing methanol in the presence of 1,5-diphenyl-1,4- BROMAMINE T
pentadien-3-one, produced N-(p-tolyl)-N-(p-tosyl)-benzamide
via addition of 2 eq. Chloramine T to the intermediate Bromamine T is the brominated analogue of Chloramine
followed by extrusion of sulfur dioxide. The 1,5-diphenyl-1,4- T. It has been used for aziridination of olefins in the presence
pentadien-3-one remained intact in the course of reaction of palladium (Scheme 132) [176]. The proposed mechanism is

Ar'' N Ph
Chloramine T N
ArCOCH=CHSO2Ar' + Ar''CH=NNHPh
MeOH
ArCO SO2Ar'

Scheme 129

OH
H N O O N SO2NH2
SO2

+ Chloramine T
MeOH +
Ph Ph
Cl Cl

Scheme 130

Cl NHTs
1) CO2 (10 atm)
Ts PhH, r.t., 6 h
+ Cl N +
R Na 2) Na2SO3 NHTs Cl
R R

21 22

Yield (%)
Entry R
21 22
1 NO2 (21a) 71 (22a) 0
2 Cl (21b) 74 (22b) 0
3 Me (21c) 54 (22c) 9
4 MeO (21d) 0 (22d) 76

Scheme 131

159
Application of N-Halo Reagents in Organic Synthesis

shown in Scheme 133. are prepared easily starting from saccharin [179].

R1 X R1 X R1 X O
TsNBrNa, Pd (II) R2
+
R2 MeCN, rt R2 N TsHN Br N X
Ts S
2.5-81% 7-19% O
O
Ts : CH3C6H4SO2
R1, R2 = Alkyl or Aryl, X: COOMe, CONMe2, CN, X= Cl, Br, I
COMe, CO(CH3)2, SOPh, Ph, or CH2OH.
23
Scheme 132
NCSac has been shown to undergo electrophilic-Ritter
type reaction with alkenes in acetonitrile. These reactions have
Br
NMe2
Ts N NMe2
been carried out at -42 C up to room temperature and two
TsNBrNa Cl Pd different products have been obtained (imidazoline or
Cl Pd O -NaCl O
Cl aziridine) (Scheme 135) [180].
O
Ts
N SO2Ar
NMe2
1.1 eq. NCSac N
Ts N Pd Cl -PdClBr MeCN, -42 C
NMe2 N N-SO2Ar
Br O R +
then KOEt R
Scheme 133 EtOH,-42 C to r.t.
R
Ar = 2-EtO2CC6H4- R = Aryl
Both Fe() and Mn-porphyrin complexes are effective
catalysts for aziridination of alkenes using Bromamine T, the Scheme 135
reaction proceeded with moderate to low stereospecificity
(Scheme 134) [177,178]. N-halosaccharines have been used for regioselective
cleavage of epoxides into vicinal halohydrins and dihalides in
the presence of Ph3P (Scheme136) [181].
Ts
R1 R3 N
Bromamine T, Cat. R1 R3
R2 MeCN, r.t.
R2 O NXSac (1.2/1.2) X= Br, Cl, I
PhO PhOCH2CH(OH)CH2X
r.t., 1% aq. CH3CN, 3-40 Min
Catalyst = Fe(Por)Cl or Mn Complex
15-95%
R1, R2, R3 = Alkyl or Aryl
NXSac (2.5/2.5)
PhOCH2CHXCH2X
Scheme 134 O reflux, CH3CN
X= Br, Cl,
PhO (75-90%)
X'= Br, Cl, I
NXSac (1.2/1.2)
PhOCH2CHX'CH2X
NX'Sac (2.5/2.5), reflux, CH3CN
N-HALOSACCHARINES
Scheme136
N-halosaccharines proved to be useful and alternative
reagents for diverse organic transformations, such as
halogenation of aromatic compounds, co-halogenation of Chlorinated and brominated aromatic compounds were
alkenes, oxidation of alcohols, halogenation of benzylic and - prepared selectively by reaction of electron-rich aromatic
carbonylic positions, etc. N-Chloro-, N-bromo- and N- compounds with NCSac or NBSac in good yields at room
iodosaccharin, 23 (NCSac, NBSac, and NISac, respectively) temperature (Scheme 137) [182].

160
Kolvari et al.

G G
Sanchez and Fumarola reported an efficient method for
NXSac benzylic and -carbonylic bromination using NBSac under
MeCN, rt
X mild conditions (Scheme 139) [184].
X= Br or Cl

Scheme 137
CH3 CH2Br

Dolenc reported iodination of enole acetates and 1,3- NBSac, 5% Benzoylperoxide


dark, 80 C
diones with NISac yielding the corresponding -iodoketones 2 h, 76%
and 2-iodo-1,3-diones (Scheme 138). Reactions were carried
out at room temperature under neutral condition in good yields Scheme 139
and short reaction times [183].
NBSac has successfully been used for chemoselective
OAc O oxidation of thiols to their corresponding disulfides in
R1 NISac R1 dichloromathane under microwave irradiation in high yields
R3 R3
15 min to 6 h I
R2
R 2 (Scheme 140) [185]. Two mechanisms were proposed for
70-90%
these reactions that both are shown in scheme 141.
R1, R2 , R3 = Alkyl or Aryl

O O NBSac
O O R-SH RS-SR
NISac CH2Cl2, MW
R1 R2 R1 R2 3-10 min
15 min to 6 h
I 86-94%
70-90%
R= Aryl or Alkyl
R1, R2 , R3 = Alkyl or Aryl
Scheme 140
Scheme 138

Ionic mechanism:
O O

R-SH + N Br N R S Br
S S
O O H
O O
I II
O

II NH + R S Br
S
O
O

2R S Br RS-SR + Br2

Radically mechanism:

O O

N Br NH
R-SH + + R S Br
S S
O O
O O

R-SH + R S Br RS-SR + HBr

Scheme 141
161
Application of N-Halo Reagents in Organic Synthesis

NBSac was applied as an efficient reagent for the oxidative The reactions of NCSac and NBSac with alkenes
cleavage of oximes to the corresponding aldehydes and (cyclohexene, styrene, -methylstyrene, and 1-hexene) gave
ketones under microwave irradiation with reasonable yields the corresponding halohydrins in H2O and acetone as solvent
[186]. The same group has reported the above transformation (Scheme 144) [188].
with NBSac in water and acetone as solvent at room
temperature or by conventional heating or microwave
irradiation (Scheme 142) [187]. R1 R1
NXSac X
2 3 H2O/Me2CO HO
R R R2 R3
10-45 min
71-93%
NOH O X = Cl or Br
NBSac
R 1
R acetone, H2O R1
2
R2 R1 = n-Bu, Ph
r.t, reflux or MW R2 = H
R3 = H, Me
R1, R2= Alkyl or Aryl
Scheme 144
Scheme 142

Bromination of 7,8,9,10-tetrahydrobenzo[a]pyren-7-ol was


NCSac and NBSac were successfully applied for
selectively carried out with NBSac (Scheme 145 ) [189].
halogenation of electron rich aromatic compounds (anisole,
acetanilide, N,N-dimethylaniline) [188]. The reaction with
NBSac gave para-substituted compounds only, whereas
NCSac produced a mixture of ortho and para isomers
(Scheme 143). NBSac
r.t., 24 h,CH2Cl2

OH Br
G G OH
product ratio : 66% (6-Bromo)/34% (other isomers)
NBSac Scheme 145
MeCN, r.t.
5-10 min
60-77%
Br Aloui and Fairbanks have reported glycosylation reactions
by NISac in the presence of acetone and methanol for
G G
stereoselective production of acetal-linked -glycosides
NCSac (Scheme 146) [190].
MeCN, r.t.
30-110 min NBSac and NISac reacted with electron-deficient alkenes
53-79% Cl
such as ,-unsaturated ketones, acids, esters and nitriles in
p/o ca. 4.5/1 aqueous organic solvents, yielding the corresponding
halohydrins in good yields (Scheme 147) [191]. The reactions
G =H, -OMe, -NHAc, -NMe2

Scheme 143

BnO BnO
BnO O O
NISac, MeOH (3 eq), acetone BnO
SPh
BnO -78 to 0 C, 2.5 h, 76% BnO
OBn
OBn O OMe

Scheme 146

162
Kolvari et al.

NOH O
took place at room temperature, mostly within short reaction NBP
1
R R2
acetone, H2O 1
R2
times and with high anti stereoselectivity. R
r.t.
R1, R2= Alkyl or Aryl

Scheme 148
OR OR
Y NBSac or NISac Y
Ph Y
Ph solvent, ROH or Ph An interesting example of the chemoselectivity of these
41-97% Br I reactions includes deoximation in the presence of primary
Y = COMe, COPh, CO2H, CO2Me, CN benzylic alcohols (Scheme 149).
R = H, Me, Et,
solvent : CH3CN or acetone/H2O Similar reactions were also carried out under microwave
irradiation in very short times [193]. NBP has been used for
Scheme 147
the oxidation of various organic compounds in the presence of
mercuric acetate as well as in acetic acid medium. Among
them, kinetic studies were carried out for the oxidation of
N-HALOPHTHALIMIDES
glycylglycine [194], aromatic aldehydes [195,196],
acetophenone derivatives [197,198], aliphatic amines [199], -
N-Halophthalimides (NXP) have been used in organic
hydroxy acids [200], and aspirin [201]. NBP was used for the
synthetic methodology especially in the oxidation and
facile oxidation of thiols to symmetrical disulfides in a
bromination reactions. In most cases these reagents are
mixture of acetone-water under microwave irradiation [202].
converted to phthalimide in the end of reactions, as a nontoxic
Both aromatic and aliphatic thiols were selectively oxidized in
chemical.
good to excellent yields (Scheme 150).
N-Bromophthalimide NBP
RSH RS-SR
N-Bromophthalimide (NBP) has been found to be an acetone, H2O
MW
efficient and selective reagent for the mild oxidative cleavage
R = Aroamtic, Aliphatic
of oximes to yield the corresponding carbonyl compounds in
good to excellent yields (Scheme 148) [192]. Scheme 150

NOH O
OH OH
+ NBP
+
acetone, H2O
r.t.
91% 99%

Unchanged alcohol

Scheme 149

R O R O

Et2O
+ N Br + NH
r.t.
72-90%
O O
Br

R = OCH3, NHAc, NEt2, OH, CONH2

Scheme 151
163
Application of N-Halo Reagents in Organic Synthesis

Reaction of substituted benzene rings with NBP, under NCP was successfully used in the first step of the ring
neutral conditions, gave the corresponding bromo derivatives expansion of peniciline V sulfoxide p-nitrobenzyl ester 24 to
with a preference for the formation of para over the ortho 3-exomethylene cephalosporin V sulfoxide p-nitrobenzyl ester
isomers (Scheme 151) [203]. NBP has also been used for the 25 (Scheme 153) [206].
bromination of some deoxyhexoses [204].
N-FLUORO REAGENTS
N-Chlorophthalimide
The photoinitiated free radical chlorination of The development of mild and selective methods for
hydrocarbons with N-chloro-phthalimide (NCP) has been introduction of fluorine into organic substrates is an important
reported [205]. Some evidence led authors for the suggestion objective because this element exerts unique influences upon
of the chlorination mechanism (Scheme 152). physical, chemical, and biological properties. Until quite
recently, however, the selective electrophilic fluorination of
O O enolates and carbanions was difficult because most procedures
h employed highly reactive, corrosive and toxic materials such
N Cl N + Cl
as F2, FC1O3, or MeC(O)CF3 . To overcome these limitations,
O O a range of N-fluoro reagents with different reactivities, that
O O were safe and easy to handle without special equipment, was
developed [207]. These reagents are easy to handle but have
RH + N NH + R
low reactivity [208]. Recently, fluorous biphasic and triphasic
O O systems has been developed so that catalysts which has
perfluoroalkyl groups as tags are soluble in perfluoro solvents
O O and insoluble in virtually all common organic solvents
[209,210]. We think that N-fluoro reagents may be effectively
R + N Cl N + RCl
used in the above mentioned systems in future. Several
O O reviews concerning N-fluoro reagents have been published
[211,213]. Therefore in this article some recent applications of
Scheme 152

O
O H H
H H
V SCl
V S
CH3 NCP, toluene
N
N CH3 Polyvinylpyridinedivinylbenzene O CH3
O
CO2PNB CO2PNB

24

O
H
V S
1) SnCl4
N
O
2) MeOH
CO2PNB

25

V= PhOCH2CONH
PNB= p -Nitrobenzyl

Scheme 153

164
Kolvari et al.

F
N-fluoro reagents are reviewed. Sniekus et al. have reported F
flouroniation of aromatic compounds by N- [F+]
+
fluorobenzensulfonimide (NFSi) and N-fluoro-o-
F
benzenesulfonamide (NFOBS) via direct ortho metallation
Scheme 156
(Scheme 154) [214].

R R R
SO2NHMe SO2NHMe F
Br Br F F Br
F
2 eq n-BuLi 1) n-BuLi, -78 C +
THF/ -40 C 2) NFSi
N N N
NFOBS
Me Me 20-78% 4-24%

71% O
R = -OCH2OCH3,
Scheme 154 O

Hiyakawa et al. have reported fluorination of indols using Scheme 157


NFSi and a directed metallation group (Scheme 155) [215].
1-Fluoro- and 1,3-difluoroazulenes were synthesized for Laulo et al. have shown that N-fluoro-2,4-dinitroimidazole
the first time by the electrophilic fluorination of azulenes with can fluorinate several classes of polycyclic aromatic
N-fluoro reagents such as NFSi, N-fluoro pyridinium salts, hydrocarbons (PAHs) (Scheme 158) [218].
selectfluor and accufluor (Scheme 156) [216]. Banks et al. reported preparation of some N-fluoro
NFSi has been applied for the synthesis of novel 3,5- reagents [219-221]. These reagents have been used for
difluoropyridine-4-carboxaldehyde in good to high yields at fluorination of various organic compounds (Scheme 159).
-120 C to -78 C. Maintaining the low temperature during the A regioselective method for the fluorination of
trans metallation was found to be critical for the selective dibenzofuran diphenylether and biphenyl with different N-
formation of difluoro over monofluoro derivatives (Scheme fluoro reagents has also been reported [222]. A typical
157) [217]. example for fluorination of dibenzofuran by three different

F
Li
H3CO NMe2 NMe2 NMe2
H3CO
H3CO
t-BuLi/pentane NFSi/THF
N -78 C to 0 C 0 C, 2 h N
N
TIPS 40% TIPS
TIPS

TIPS = triisopropylsilylgramine
Scheme 155

NO2 F

N F reflux, 3 day F
+ +
C2H4Cl2, 20 mL
O2N
23%

9:1
Scheme 158
165
Application of N-Halo Reagents in Organic Synthesis

Cl
N N
R R n
Cl N Cl N
F S S O n
BF4 F CF3SO2
F + +
R1 R2 CH2Cl2/ THF/ H2O R1 R2 S S N
H F
R = -NO2, -Cl, -OMe 1 2
R , R = Alkyl or Aryl

Scheme 159
Scheme 162
N-fluoro reagents is shown in Scheme 160.
groups [238-239] to achieve a broad range of -fluorinated
Modified nucleosides have become useful agents for the
organic compounds such as -fluorosulfonamides, -
treatment of cancer and viral diseases due to their good
fluorolactams, -fluoroketones, etc. Various N-alkylimines
antitumor and antiviral activity. In particular, several
derived from acetophenones were successfully
nucleosides with substituents at 4'-position are good
monofluorinated using NFSi in a mixture of acetonitrile and
candidates as antiviral agents. 4'-Fluoro nucleoside is one of
DMF at 0 C. Alternatively, the same procedure in the absence
these moieties that have strong activity including anti-HIV
of DMF gave rise to diflourinated imines when performed at
activity. Jung and Toyota have synthesized 4'-
room temperature. The obtained -fluoro and ,-difluoro-
fluorothymidines using NFSi as fluorinating agent (Scheme
imines were subsequently reduced to give the corresponding
161) [223].
-flouro and ,-diflouroamines (Scheme 163) [237].
O O
NH NH i-Pr
O N
N O N O
3.4-4 eq. i-PrNH2 1.2 eq. NFSI
ButO2C 5.5 eq LDA 0.6 eq. TiCl4 2.0eq. K2CO3
O 4.5 eq t-BuLi F O
Et2O, r.t., 15 h
NFSi ButO2C
OH OH 62% (E/Z 62: 38)
i-Pr
Scheme 161 N O
F F
aq. 2M HCl
CH2Cl2, r.t., 2.h
N-Fluoro-2,4,6-trimethylpyridinium triflate efficiently
cleaved dithioacetals to the parent carbonyl compounds
(Scheme 162) [224]. 91%

An important application of N-fluoro reagents is Scheme 163


fluorination of activated methylene [225-237] and enolate

O O O O F
F-L
+ +
F
F

fluorinating reagent F N N CH2Cl F N N OH


strucrure (F-L) Cl Cl
N
- (BF4-)2 F
(BF4 )2 BF4-

Scheme 160

166
Kolvari et al.

N-HALOAMINES Oxidation of urazoles and bis-urazoles was carried out


with 27. The in situ generation of Cl+ appeared to be vital for
There are few papers concerning the utilization of N-halo the oxidation of urazoles using this reagent [244].
amines in organic synthesis. Generaly N-halo amines can be
viewed as a source of halonium ions. There are only few N-
halo amines such as trichloromelamine and N,N,2,3,4,5,6-
NH2 NCl2
heptachloroaniline that can be used as a chloronium ion NCl
Cl Cl Cl Cl
Cl Cl
source. Trichloromelamine (TCM, 26), is a source of HOCl I2, CCl4

chloronium ion because the 1,3,5-triazine ring has strong Et2O room temp.
Cl Cl Cl Cl
Cl Cl
electron-withdrawing character. However, there are few Cl Cl Cl Cl
papers concerning the utilization of TCM in organic synthesis 27 28
[240-241].
Scheme 165
NHCl

N N
N-HALOSUCCINIMIDE
ClHN N NHCl

26
Some specific properties of N-halosuccinimides (NBS,
NCS and NIS) cause their wide application in organic
Kondo et al. have reported a simple and selective method synthesis. The scope of the application of N-halosuccinimides
for the oxidation of alcohols to the corresponding carbonyl is so wide that needs a special review for covering their
compounds and oxidative lactonization of diols with TCM in chemistry. The recent application of NBS as a catalyst,
methylene chloride at room temperature under mild conditions oxidant, selective brominating reagent and the initiator in the
(Scheme 164) [242]. polymerization has been reviewed [245]. Although two
excellent review articles have been published on this subject
[1,245] we think that publishing a new review for covering the
HOCH2(CH2)nCH2OH TCM
(CH2) n O new applications of these compounds in organic synthesis is
CH2Cl2, r.t.
O
necessary. N-Hallosuccinimides are commercially available
R1 R1
and extensively had been used in many fields of fine organic
TCM
CHOH C O synthesis and at natural compounds chemistry as well [1].
R2 CH2Cl2, r.t. R2
Therefore, due to the above mentioned facts we decided to
avoid reviewing the recent application of N-halosuccinimides
R1, R2 = H, alkyl or aryl
in the present manuscript. However, we are preparing a review
n= 2, 3
article on this subject that will be published in near future.
Scheme 164

O
N,N,2,3,4,5,6-Heptachloroaniline 27 and N-chloro-
2,3,4,4,5,6-hexachlorocyclohexa-2,5-dienylideneamine 28 N X
(Scheme165) can be used as chlorinating agents. Compound
28 was used as a new mild and highly regioselective O
chlorinating reagent in the chlorination of phenol and o-cresol NBS: X=Br
NCS: X=Cl
in CCl4, DMF and CH3CN. The effects of C2H5OH, C5H5N, NIS: X=I

DMF, and Et3N on the regioselectivity in CCl4 have been


examined [243].

167
Application of N-Halo Reagents in Organic Synthesis

O
O
X Y O O
N N X Y
N N S N (CH2)n N S
O N O R'
R O X Y O
Z O
XY R=R' or RR'
XYZ XY X= Br, Cl, I
X=YZ X= Cl, Br or I Y= Br, Cl, I
XY=Z Y= Cl, Br or I
X= Cl, Br or I
Y= Cl, Br or I
Z= Cl, Br or I

Scheme 166

CONCLUSIONS Kaishi 11 (2000) 749.


[5] T. Umemoto, S. Fukami, G. Tomizawa, K. Harasawa,
It should be noted that a correct and updat citation and K. Kawada, K. Tomita, J. Am. Chem. Soc. 112 (1990)
literature survey is very important for researchers to find 8563.
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