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Dr. Bapu R.

Thorat
Assit. Professor of Chemistry
Govt. of Maharashtra,

Ismail Yusuf Arts, Science and Commerce College, Jogeshwari (E),


Maharashtra 400060

Reagent

Reagent & Reaction


cond.

Substrate

Product

A group of organic molecules serve as substrates for a particular type of reaction


when treated with specific reagent.
e. g. Nitration of aromatic compounds by using nitrating mixture; the aromatic
compounds are substrates and nitrating mixture is reagent for nitration reaction.

Types of reactions

1.
2.
3.
4.

Addition reaction;
Elimination reaction;
Substitution reaction;
Rearrangement;

1. Pericyclic reaction;
2. Photochemical and
radical reaction;
3. Oxidation;
4. Reduction

free

Nitration

Bromination
Sulfonation

Carbonylation

Halogination
Acylation

Alkylation

Formylation

Oxidation

Oxidation of an organic compound involves


one or more of the following changes:
(1) an increase in the multiple bond order of
the C
(2) addition of O to a C
(3) replacement of an H on a C by O.

Reduction

Reduction of an organic compound involves


one or more of the following changes:
(1) an decrease in the multiple bond order of
the C
(2) addition of H to a C
(3) replacement of an O on a C.

Oxidizing agents

Cr(VI) Reagents: Sodium or potassium dichromate (Na2Cr2O7 or K2Cr2O7), or


chromium trioxide (CrO3), to aqueous solutions of sulfuric or acetic acid.
Modified reagents: PCC (Pyridinium chlorochromate); PDC (Pyridinium
dichromate); chromium trioxide pyridine (CeO3.py2);
MnO2

KMnO4

O2

Sodium Hypochlorite
(NaOCl)

Peroxycarboxylic acids

selenium dioxide (SeO2)

H2O2/NaOH

Triiosproxide aluminium
Oppenauer oxidation

Osmium tetroxide
(OsO4)
Pb(OAc)4

Jones
reagent

DMSO/oxalyl chloride:
Swern oxidation
Ozone (O3)
HIO4

chromyl chloride
(Cl2CrO2)
Fremy's salt ((KSO3)2N-O.)

K3[Fe(CN)6]

Reducing agents
Metals used for reduction: Copper (low valent), Chromium (low valent), Fe, Indium (low
valent), Iron, Lithium, Magnesium, Manganese, Neodymium (low valent), Nickel, Niobium
(low valent), Potassium, Red-Al, Sodium, Strontium, Titanium (low valent), Zinc, Samarium.

Hydrides: Potassium tetrahydroborate, Potassium borohydride, Sodium borohydride, Sodium


cyanoborohydride, Sodium tetrahydroborate, Sodium triacetoxyborohydride, Decaborane,
Diisopropylaminoborane, Dimethylsulfide borane, Diborane, LiTEBH, Nickel borohydride

Sodium

bis(2-methoxyethoxy)aluminumhydride,

DIBAL-H,

LAH,

Aluminium

triisopropoxide/isopropanol

Tin hydrides, Tributyltin hydride


Tributylstannane,
Trichlorosilane, Silanes, Triethylsilane, Tris(trimethylsilyl)silane, Diethoxymethylsilane

Zirconocene chloride hydride


Copper hydride
Hydrogen
Formic acid

Hydrazine

Sodium dithionate

Organometallic reagents in organic synthesis


Organometallic chemistry timeline
1827 Zeise's salt is the first platinum-olefin complex: K[PtCl3(C2H4)]H2O Zeise's salt
1863 C. Friedel & J. Crafts prepare organochlorosilanes
1890 L. Mond discovers Nickel carbonyl
1899 Introduction of Grignard reaction
1900 P. Sabatier works on hydrogenation organic compounds with metal catalysts:
Hydrogenation of fats
1909 P. Ehrlich introduces Salvarsan for the treatment of syphilis, an early arsenic based
organometallic compound. (As3Ar3) [Ar 3-amino-4-hydroxypheny]
1912 Nobel Prize: Victor Grignard and Paul Sabatier
1930 Henry Gilman works on lithium cuprates: RX + 2Li
RLi + LiX
1951 Ferrocene is discovered
1963 Nobel prize for K. Ziegler and G. Natta on Ziegler-Natta catalyst
1965 Discovery of cyclobutadieneiron tricarbonyl Ferrocene (C4H4)Fe(CO)3
1968 Heck reaction
1973 Nobel prize G. Wilkinson and E. O. Fischer on sandwich compounds
2005 Nobel prize Y. Chauvin, R. Grubbs, and R Schrock on metal-catalyzed alkene
metathesis
2010 Nobel prize Richard F. Heck, Ei-ichi Negishi, Akira Suzuki. "for palladium-catalyzed
cross couplings in organic synthesis"

Organometallic reagents in organic synthesis

Materials which possess direct, more or less polar bonds M+C- between metal
and carbon atoms.

In addition to the traditional metals, lanthanides, actinides, and semimetals,


elements such as boron, silicon, arsenic, and selenium are considered to form
organometallic compounds.

e.g. Organoborane compounds such as triethylborane (Et3B).

Organometallic chemistry combines aspects of inorganic chemistry and organic


chemistry.

Classification of organometallics based on the bond type:

Organometallic reagents in organic synthesis

Covalent, multicenter,
-bonded

Organo borane compounds


Organoborane or organoboron compounds are organic derivatives of BH3. Organoboron
compounds are important reagents in organic chemistry enabling many chemical
transformations, the most important one called hydroboration.
Characteristics:

C-B bond, low polarity (electronegativity C 2.55, B 2.04)

Electron-rich groups like vinyl or phenyl provide the C-B bond with partial
double bond character.

Organoboron hydrides R2BH and RBH2 form dimers which always display
hydride bridges rather than alkyl bridges.

Organo borane compounds


Hydroboration: Synthesis of alkylborane (mono, di, tri-)

Borane (BH3 in dimer form) reacts rapidly to alkenes and alkynes forming alkyl and alkenyl
boranes are called as called hydroboration. This concept was discovered by Herbert
Charles Brown at Purdue University with help from George Wittig.
Number of alkenes of widely different structures except most hindered alkenes.
The simple alkenes gives (mono- and di-substituted ethylenes) gives trialkylborane.
Tri-substituted ethylenes gives dialkylborane, and
Tetra-substituted ethylenes forms monoalkylboranes.
The mono- and di-alkylboranes are less reactive and more selective than the borane
itself.
More substituted C has +
+

Less substituted C has -

Asymmetric alkenes
In case of allyl derivatives and nuclear substituted styrenes, the proportion of product
formed by addition of boron to the -carbon (more substituted carbon) atom increases with
the electronegativity of the substituents.

Organo borane compounds


CH3(CH2)3CH=CH2
6% 94%
CH2=CHCH3

(CH3)2C=CHCH3

CH3CH=CH(CH3)2

2% 98%

58% 42%

CH2=CHCH2OC2H5

CH2=CHCH2Cl

19%

94% 6%

40%

CH3O

82%

Cl
25%

18%

5%

Mechanism

Hydroborations take place stereoselective in a syn mode that is on the same face of the
alkene. The reaction proceeds through transition state is represented as a square with the
corners occupied by carbon, hydrogen and boron with maximum overlap between the two
olefin p-orbitals and the empty boron orbital.

+
H B

solvent

protonolysis
H B

Organo borane compounds


Hydroboration: Synthesis of alkylborane (mono, di, tri-)
+

alkene

organoborane

+
alkyne

alkylborane

H
H

B
H

H3C
2

CH3

B2H6/THF

H3C

CH3

H3C

CH3

organoborane
alkenylborane

e.g. H C
3
1

Hydride source

[(CH3)2CH-CH(CH3)]2BH
disiamylborane

B2H6/THF

[(CH3)2CH-C(CH3)2]BH2
thexylborane

B2H6/THF

B-H

3
B2H6/THF

9-BBN
no reaction because of steric hinderence

The hydroboration of alkenes and alkynes is highly stereospecific and takes place by addition to
the less hindered side of the multiple bond.

Organo borane compounds


Hydroboration: Limitations
1. The regio-selectivity in the hydroboration of terminal alkenes, although high, is not
complete and in 1,2-disubstututed alkenes there are little discrimination between the
two termini of the double bond.
2. There is little difference in the rate of reaction of borane with differently substituted
double bonds, so that it is rearly possible to carry out selective hydroboration of one
bond in presence of another.
3. The hydroboration of terminal alkyne is difficult to controlled at the single addition but
the desired alkenylborane undergoes second addition of a second molecule of borane to
the 1,1-dibora-alkane.

Problems:
1-alkylcycloalkanes on hydroboration followed by oxidation gives 4-chlorostyrene on hydroboration followed by oxidation gives 4-chlorostyrene on hydroboration followed by heating and then oxidation gives -

Hydroboration of 2-pentene gives (i) on protonolysis (ii) oxidation, (iii) heat and then
oxidation

Organo borane compounds


From Grignard Reagent: Synthesis of alkylborane (tri-)
This method is generally used for the synthesis of trialkylborane such as trimethylborane and
triethylborane.
3 RMgX

BX3

R3B

+ 3 MgX2

By exchange method: Synthesis of alkylborane (tri-)


The organoborane exchange their alkyl group with more reactive alkene alkyl.
R3B

+ 3 Alkene
more reactive

R'3B

+ 3 Alkene'
less reactive

Isomerisation:
The organoborane compounds undergo isomerisation on heating if and only if -carbon atom with respect
to boron atom bearing atleast one hydrogen atom. Such organoborane compound undergoes isomerisation
to stable organoborane compound (to organoborane compound in which boron has less substituents) by
addition-elimination mechanism.
B
H

e.g.

BH3

THF

B
o

200 C

Organo borane compounds


Organo-Borane Reagents used organic synthesis
Many of these reagents, such as thexylborane, disiamylborane, dipinylborane, 9-borabicyclo[3.3.1] nonane, catecholborane, chloroborane etherates, haloborane-dimethyl sulfides,
IPCBH2, ICP2BH, RBCl2 and R2BCl.
[(CH3)2CH-CH(CH3)]2BH

[(CH3)2CH-C(CH3)2]BH2

disiamylborane

thexylborane

B-H
9-BBN

O
BH
O
catecholborane

H2BX

[(CH3)2CH-C(CH3)2]BHCl

monohaloborane
dihaloborane
(X- Cl, Br)
BH2

mono-isopinocampheylborane
[ICPBH2]

HBX2

) BH
2

di-isopinocampheylborane
[ICP2BH]

thexylmonochloroborane

Organo borane compounds: Disiamylborane


It is dialkylborane used selectively for the hydroboration of C=C bond in such a way that
boron atom attach to less stericaly hindered carbon. It is used selectively for
monohydroboration of alkynes.

Preparation:
H3C
H3C

CH3

B2H6/THF

[(CH3)2CH-CH(CH3)]2BH

disiamylborane

2-methyl-2-butene

Steric interactions between methyl and


Siamyl group

Examples:

B(C5H11)2
e.g.1.

[(CH3)2CH-CH(CH3)]2BH

+
B(C5H11)2
3%
B(C5H11)2

2,

[(CH3)2CH-CH(CH3)]2BH

oxidation

97%
OH

Organo borane compounds: 9-BBN


It is more sensitive to the structure of the alkene. Terminal alkenes react more rapidly than
the internal alkene and Z-alkene also react more rapidly than the E-isomer.
These are also used for monohydroboration of alkynes which on oxidation to ketone. The
acid catalyzed hydrolysis of terminal alkyne gives methyl ketone while by using
disiamylborane or 9-BBN followed by oxidation gives aldehyde.
These reagents are used to reduce mono- and di-substituted alkene preferentially than
the tri- and tetra-substituted alkene.
The same result is obtained by using catacholborane, dibromoborane or
thexylmonochlorborane.
B-H
BH3/THF

e.g.

e.g.1.

H5C2

2.
H5C2

H-B

B-H

R'

C2H5

9-BBN
THF

9-BBN
THF

9-BBN
THF
H5C2
H

R'

H5C2
H
H
B

C2H5

protonolysis

oxidation

R'

H5C2

B
oxidation

H
H5C2
H

C2H5
OH

H
H5C2-CH2CHO
OH

Organo borane compounds: Thexylborane


It is most radialy available of monoalkylborane. It is useful for cyclic hydroboration of
diene. Hydroboration of diene itself by using borane gives polymer but with thexylborane
gives cyclic or bicyclic organoboranes.

Thexylborane is also used for the synthesis of trialkylboranes containing three different
alkyl groups. This process has limited scope because the first alkene must be relatively
unreactive.
This difficult can be overcome by using thexylchloroborane The thexylchloroborane react
with an alkene gives an chloroalkylthexylborane which may be converted to
dialkythexylborane by reaction with one equivalent Grignards reagent or an alkyl-lithium
or by hydridation with LAH in presence of alkene.
Dialkylthexylboranes are useful for the synthesis of cyclic or acyclic ketones.
H3C
H3C

CH3

B2H6/THF

[(CH3)2CH-C(CH3)2]BH2

CH3

thexylborane

2,3-dimethyl-2-butene
e.g.1.

Thexylborane
THF

1.CO

NaBH4

2. H2O/OH

OH

COOEt
2.

Thexylborane
THF

H
B

COOEt
1.CO
2. H2O/OH

COOEt

Organo borane compounds: Optical active reagents (Ipc2BH and IpcBH2)

Diisopinacamphenylborane (Ipc2BH) and monopinacamphenylborane (IpcBH2) are prepared


in either form by reaction of borane with (+) or (-)--pinene under appropriate conditions.
These reagents are used for the synthesis of optical active alcohols.

BH3

BH

THF
(+)-a-pinene

H
purification with 15% a-pinene and stand it over
night

BH

BH2

a-pinene
TMEDA
IPCBH2

IPC 2BH
100%ee

IPC 2BH 93% ee

100%ee

The Z-alkene is converted into optical active secondary alcohol of high optical purity by using
Ipc2BH followed by oxidation. But with E-substituted alkene best result will obtained by using
IpcBH2, the success of reaction is depends on the bulk of the alkyl substituents of the double
bond.

)2BH

)2B

H2O2/NaOH

HO

H
BH2

H
B

H2O2/NaOH

H
(R, 87% optical pure)
H
HO

H
(S, 73% optical pure)

Reactions of organoboranes

Protonolysis
Protonolysis of organoborane compounds by using organic acid is the convenient method for
the reduction of carbon-carbon multiple bonds.
Alkenylborane are more reactive than the alkylborane. This
reaction takes place with retensation of configuration at the
carbon atom attach to the boron atom. The alkynes are cleanly
converted into Z-alkenes.
R
R B
R

H
R
+
R B O
R

H
O

R'

R'

R-H

Boiling with propaonic acid


At RT with acetic acid

R2B(OCOR')

2 R-H + B(OCOR')3

Advantageous - the reduction of the double bond or triple bond in compound containing
other reducible functional groups can be easily occurs such as compounds containing ester,
sulphide, protected carbonyl group, nitro group, etc
C4H9
1.

2.

CH2

C2H5

BH3/THF

C2H5

(C5H11)2BH
Diglyme

(C4H9CH2CH2)3B
C2H5
H

C2H5
B

propionic acid
reflux
CH3COOH
o
25 C

C2H5
H

C4H9CH2CH3

91%

C2H5
H

68%, almost Z-isomer

Reactions of organoboranes

Protonolysis

Diastereoselective hydration of the double bond of acyclic alkenes.


RL

CH3 RM H

1. R2BH
2. H2O2/NaOH

RM

RL

H3C H RM H
major

H CH3
minor

RL

Terminal alkene in which RL and RM are stericaly large and medium sized substituent
groups respectively. The stereochemistry of the hydroboration appears to be controlled
primarily by the size of the groups on the nearby chiral carbon.
CH3

e.g.
H3C

CH3
1. thexylborane
2. H2O2/NaOH H3C

CH3

CH3

CH3

CH3

OH

OH

H3C
OH

OH
(81%, 6:1 selectivity)

Intramolecular hydroboration takes place via boat


like transition state rather than the chair. The
formation of boat like transition state is preferred
because the boron-hydrogen bond eclipses the system of the double bond but it is not a case in chair
form formation. This indicates that intramoleculer
hydroboration reaction takes place through planar four
membered transition state.

H
H3C
B
H
boat transition state
is preferred.

H3C

B
H

chair transition state


not prefered.

Reactions of organoboranes

Oxidation
Oxidation of organoboranes to alcohol can be easily carried out by using alkaline
hydrogen peroxide.
In overall reaction the water molecule can be added (overall is cis-/syn-addition) across
the double bond by using anti-Markownikoff rule. This also used to convert alkyne into
ketone and aldehyde (by using terminal alkyne) rather than to the methyl ketone.
R
R B
R

H
R
R

B-

R
O

OH

B O

OH
R

R
R

-B O

B O
R

O R

+ ROH

ROH + B(OH)3

H2O2 + NaOH

The reaction path involving intramoleculer transfer of alkyl group from boron to carbon in
an intermediate ate compound.
CH3
1.

OH
1. (C5H11)2BH / Diglyme
2. H2O2/NaOH

CH3
CH3
2.

CH3
CH3

1. (C5H11)2BH / Diglyme
2. H2O2/NaOH

OH
CH3
H

OH
CH3
H
CH3
OH
CH3

Reactions of organoboranes

Oxidation
The direct oxidation of primary trialkylborane into aldehyde and secondary
trialkylborane into ketone, without isolation of the alcohol is possible by using pyridinium
chlorochromate (PCC) or aqueous chromic acid.

BSia2

BSia2
PCC
or chromic
acid

Sia2BH
O
chromic
acid or

PCC
H

CHO
H

Reactions of organoboranes

Amine formation
The trialkylboranes are converted into primary amine by reaction with hydroxylamine-Osulphonic acid or N-chloroamine.dialkylchloroborane with organic azide gives secondary
amine. Only one alkyl group can be migrate towards the nitrogen atom therefore, yield of the
product is less which can be increased by using 9-BBN or Sia2BH.

R3B

H2N-Cl/H2NOSO4H

R
R

B- +

Cl

NH2

Cl -

R
B +
R
NH2

R-NH2 + R2B-Cl

.dialkylchloroborane with N-chloroamine /organic azide gives secondary amine.


R
R2B-Cl

R'N3

Cl

B
R
R'

+
N
2
N

OH

R'

R
B N
Cl

OH2

H
R N
R'

Reactions of organoboranes

Primary bromide and iodide formation


Primary bromides and iodides are also obtained by the reaction of trialkylboranes
derived form terminal alkenes with bromine and iodine in presence of base such
as NaOH, methanoic sodium methoxide, etc.
R3B

X2
bromine
or iodine

organoborane
of terminal alkene

MeONa/MeOH

R-X

BX3

primary halide

Mechanism
R
R3B

X2

R
R

+ X
X

OH

R
R

+ R
B X

R-X

R2BOH

Reactions of organoboranes

Carbonylation
The reaction of organoborane with carbon monoxide under appropriate conditions is very
important for the synthesis primary alcohol, secondary alcohol and tertiary alcohols,
aldehydes and open, cyclic and polycyclic ketones.

R3B

R
1atm.,
r.t.
R B
CO
dry atmosphere R

O
R
LiAlH(OMe)3

H2O

B
R

R
Bora-ketone

R
B

NaOH/H2O
B
H2O2

R
ketone

H
R
aldehyde

OH

NaOH/H2O

OH

R
sec-alcohol

H2O2
NaOH

HO

OH
R

NaOH

R B O
Bora-epoxide

prim-alcohol

NaOH
presence of small
amount of water &
NaOH

polymer

in presence of
some hydride
reducing
agent

OH

R
O B

OH

R NaOH
R
OH
B
R
OH2
R
O R R
monomer
tert-alcohol
O

R
R

OH

R3B with one mole of


CO

Reactions of organoboranes
R3B

Synthesis of
tertiary alcohol

RCOOR' +

CO

R
1atm., r.t.
R B
dry atmosphere R

B
R

R
Bora-ketone

High temperature
30 alcohol in high yield

R
OH
R
R
tert-alcohol

2 RMgX

dehydration

R
R B O
Bora-epoxide

R
O B R
polymer

R
OH
R
R
tert-alcohol

alkene

OH
OH

R
B
O R R
monomer
O

NaOH
OH2

Low yield

(R is bulky substituent)

The migration of alkyl group from boron to carbon atom intramoleculerly


Synthesis of trialkylmethanols: The trialkylborane react with dichloromethyl methyl ether in
presence of strong hindered base lithium triethylcarboxide.
R3B

- +
CH3OCCl2Li
THF

Cl

R
R

Li+
OMe

Cl

B
R

Cl

CR2Cl

R3C

OMe

Cl

R B

OMe

B OMe [O]

R3C-OH

B OMe [O]

R3C-OH

H3COCHCl2 + Base

..

R3B

H3COCCl
THF

R
R

OMe
+

R
B

Cl

Cl
OMe

CR2Cl

R3C

OMe

Cl

R B

E.g. Carbonilation of equimolar mixture of triethylborane and tributylborane gives after


oxidation-

Reactions of organoboranes
Synthesis of
secondary
alcohol

R3B

CO

R
1atm., r.t.
R B
dry atmosphere R

R NaOHR

OH
R B O
B
R
Bora-epoxide
HO
H2O2 NaOH
NaOH/H2O
R
R
O
OH
R
R
sec-alcohol
ketone

R
Bora-ketone

Carbonylation reaction carried in presence of small amount of


water which resist migration of third alkyl group.

alkaline hydrolysis

Unsymmetrical ketones by using mixed organoboranes prepared


thexylchloroborane (Thexyl group has very low migratory aptitude value).
BH2

alkene A

BHRA alkene B

RA

oxidation

from

thexyl

CO

or
RA

RA

B
RB

RB

OH OH
[O]

O RB

RB

RA
O

Dienes similarly used for the synthesis of cyclic ketones.


H

H
B

Thexylborane
THF

1.CO/H2O /5OoC/70atm
2. H2O2/NaOH

Thexylborane
THF

H
1.CO/H2O
2. H2O2/NaOH
H

Reactions of organoboranes
Synthesis of
primary alcohol

R3B

Carbonylation is carried out in presence of some hydride reducing


agent such as lithium trimethoxyaluminium hydride.

R
1atm.,
r.t.
R B
CO
dry atmosphere R

B
R

O
R
LiAlH(OMe)3
R

R
B

H2O2
NaOH

OH
NaOH/H2O

R
H
aldehyde
R

OH

prim-alcohol

Main disadvantage of this procedure is that only-one alkyl group of trialkylborane is


converted into the required derivative and other two are effectively wasted. This difficulty
can be overcome by the hydroboration of alkene by using 9-BBN or disiamylborane.

CH3(CH2)7

CO
CH3(CH2)7CHOH B
LiAlH(OCH3)3

LiAlH4

CH3(CH2)7CH2

H2O2
NaOH

CH3(CH2)7CH2OH

CHO
;

H2C=CHCH2CO2Et

HOC(CH2)3CO2Et

Reaction of B-alkylboronic ester with methoxy(phenylthio)methyl-lithium forming


intermediate which react with mercurous chloride, induces transfer of the alkyl group from
boron to carbon and subsequent oxidation by using alkaline hydrogen peroxide gives
corresponding aldehyde in good yield.
CH3
CH3

CH3
BBr.(CH3)2S

HBBr2.(CH3)2S
CH2Cl2

O
B

(CH3)3SiO(CH2)3OSi(CH3)3

O
LiCH(OCH3)SPh

CH3

CH3
CHO

H2O2
NaOH

CH3

OMe
B

Alkyl
shift

-B

Hg2Cl2
SPh

O
OMe

Reactions of organoboranes

Cyanation

Trialkylborane treated with sodium cyanide forming trialkylcyanoborate. Addition of one


molar equivalent of benzoyl chloride or trifluoroacetic unhydride induces two successive
migrations of alkyl groups from boron to the adjacent carbon atom of cyanide group
forming the cyclic organoborane intermediate which on oxidation without isolation gives
ketone in high yield. In presence of excess anhydride forming trialkylmethanol.
Asymmetric ketone can be easily obtained from two different alkene.

R3B

+ CN

F3C

R
R B
R

R
N
CF3

F3C

1.CF3COOH
2.NaOH/H2O
CF3

H2O2

R
OH
R
R
tert-alcohol

NaOH
R

R
ketone

R
R

F3C

O
F3C

O
CF3

F3C

R
O

CR3

NCOCF3

O
CF3

F3C

O
CF3

H2O2
NaOH

R3COH

Reactions of organoboranes

Ketone and tertiary alcohol can be synthesized by the reaction of


trialkylboranes with anion of tri(phenylthio)-methane. Two alkyl groups are
migrates from boron to carbon in the initial adduct to give an intermediate which
can further oxidized to ketone.
A third migration of alkyl group for the synthesis of tertiary alcohol can be
induced by the treatment of mercuric ion; oxidation of the product gives tertiary
alcohol.
R
X B
SPh

R
+R3B + LiC(SPh)3

+
[R B-C(SPh) ]Li
3

-B

R SPh

HO
R 2 2 R3COH
R NaOH

R
SPh
2+
Hg
SPh
PhS
or CH3O2SF

B-SPh
R

H2O2

NaOH
R

Reactions of organoboranes
Reaction with -bromoketone and -bromoester
Organoborane react radialy with -bromoketone and -bromoester in presence of
potassium t-butoxide or hindered base forming corresponding ketone and ester
respectively. The alkyl or aryl group of organoborane displaces bromine atom from its
position.
O
RCOCH2Br

t-C4H9OK

R'

B-

BR'3
R

Br

Br

R'

R'

B
R'

O
R'

t-C4H9OH
R

R'

R'

Nucleophilic substitution
Limitationsa) Organoborane having highly branched groups do not react.
b) Only-one of the three alkyl groups in the trialkylborane is used in the reaction and
remaining is wasted therefore yield of the reaction is decreased.
This difficulties are overcome by using an alkyl derivatives of 9-BBN. This reaction can be
extended to dibromoacetates and can be controlled at the -alkyl--bromoacetates or
dialkylacetates.
BH3/THF

BrCH2COOEt
t-C4H9OK / t-C4H9OH

CH2COOEt

Reactions of organoboranes
Reaction with diazo-compounds
It is nucleophilic substitution reaction of organoborane compound. The ketones and esters
are synthesized from the diazo-compound and organoborane in presence of base.
O

O
+

R3B + N2-CHCOCH3

R R B
R

R
+

N2

CH3

CH3 hydrolysis

B
R

CH3

R
O

The mechanism studies have been suggested that the migration of alkyl or aryl group
from boron to carbon atom is occurring with elimination of nitrogen gas.
It is also used for the synthesis of nitrile or cyanide derivative.
Yield of the reaction can be increased by using dialkylchloroborane instead of
trialkylborane.

Suggest the mechanism of following:

Reactions of organoboranes
Synthesis of cyclopropane
Cyclopropane or its derivatives are synthesized from dialkylborane such as thexylborane
or 9-BBN and allylic chloride in presence of base.

Sia2BH Cl
ClCH2CH=CH2
THF
B
allyl chloride

OH

Cl

HO B

cyclopropane

Reactions of organoboranes
Alkenylborane and trialkylalkynylborates are used for the synthesis of conjugated dienes
and diynes, saturated and ,-unsaturated ketones by the migration of an alkenyl or
alkynyl group from boron to carbon instead of alkyl group.
R
H

)B

I2,NaOH
THF

Et

Et

H
Et

Et

OH

B R

I Et

I
Et

R R
B
Et I

Et

Et

Et
I

Et

Et

Et

Et

R
H

BH2

Cl

C6H11

Cl

C6H11

Cl
B

HC

C4H9

C6H11

C6H11
H CH3ONa
H
H

C4H9

H
Thexylborane

MeO
B
H
H

C4H9
C2H5COOH

H2O2/NaOH C6H11
C4H9
C6H11

(C4H9)3B +

LiC CC6H5

THF C4H9 C4H9 B


C4H9

CC6H5
I

C4H9
I2
o
-78 C (C H ) B
4 9 2

C4H9

C6H5
C4H9C CC6H5
I

Reactions of organoboranes
Reaction with conjugated Aldehyde and ketones:
Trialkylboranes reacts with vinyl aldehyde or ketone, forming an ate-complex 1, in which pielectrons move with the migration of R on B to the vinyl carbon to give enolborinate 2,
which is then hydrolyzed with water to the corresponding saturated aldehyde or ketone.
The yields and conditions are changed according to the substitution at - and -position. The
yield was drastically change with -substitution.

The conjugated ester and nitriles undergoes polymerization with trialkylboranes.

Examples
C5H11
CH3CHO

C5H11
carbonylation

C2H5O B
H

C5H11

)2BH

NH2

H2O2/NaOH

H2N-Cl/THF

H
(90%ee)

BH2
1.
2.

OH
H
(92%ee)

)2

H2BBr.(CH3)2S

BBr.(CH3)2S

B
H CH
3

CH3OH
CH3ONa

)2

CH3CHO

C2H5O

+
H CH3

C4H9
O

C5H11
B

B-OCH3

Cl2CHOCH3
(C2H5)3COLi
O
H9C4

C5H11

H CH
3

CH3

1.Cl2CHOCH3/Et3COLi
C5H11
2.H2O2/NaOH
H3C

Exercise

6
7

Organocopper reagents
Organocopper compounds in organometallic chemistry contain carbon to copper chemical
bonds. e.g. R2CuLi, RCu(CN)Li or R2Cu(CN)Li2.

The first organocopper compound, the explosive dicopper acetylide Cu2C2 was
synthesized by Bottger in 1859.
Henry Gilman prepared methylcopper in 1936.
In 1941 Kharash discovered that reaction of a Grignards reagent with
cyclohexenone in presence of Cu(I) resulted in 1,4-addition instead of 1,2addition.
In 1952 Gilman investigated for the first time dialkylcuprates.

Organocopper reagents

Organocopper Compounds
,-Unsaturated carbonyl compounds have two reaction sites:
R''
R'-MgX

R'''

+
R'''
1,4-addition

R''

OMgX

R'' R'
R
(1,4- addition)

R'''

OMgX

R'
(1,2- addition)

1,2-addition

The composition of the product can be varied with sterric bulk of R in the Grignard
reagent and R group in the carbonyl compound.
Also as size of R group of the Grignard reagent increases, the amount of 1,4addition product increases.
The 1,4-addition of the Grignard reagent was proceeds though six membered
transition state, whereas the 1,2-addition reaction proceeds through four
membered transition state.
Also if electron withdrawing group attached to alkene moiety, increases the yield of
1,4-addition product.
What is the major product obtained by the treatment of Grignard reagent on ,-unsaturated
aldehyde?

Organomagnesium Compounds
Grignards Reagent: Reactivity
X
R''
R'-MgX

R'

+
R'''

R''
R'''

Mg
R
O

H3O+

R'''
R'' R'

O
R

The cuprous salts (Cu2X2) was added to the Grignards reagents forming less
reactive product such as [R2MgCu or RCu) containing copper (I) which forming
co-ordinate bond strongly with carbonyl oxygen atom in six membered transition
state. Grignard reagent shows 1,4-addition reaction with carbonyl compound except
,-unsaturated aldehyde.

Organocopper reagents: Reactions


Substitution reactions: Cuprates R2CuLi treated with alkyl halides R'-X gives the
alkylcopper compound R-Cu, the coupling product R-R and the lithium halide.
r.d.s
I

Nucleophilic
attack to RX

III

Oxidative
addition

Reductive
elimination

Order of reactivity of electrophiles: acid chlorides > aldehydes > tosylates ~ epoxides > iodides
> bromides > chlorides > ketones > esters > nitriles >> alkenes.

Oxidative coupling: coupling of copper acetylides to conjugated alkynes in the Glaser


coupling or to aryl halides in the Castro-Stephens Coupling.
Reductive coupling: coupling reaction of aryl halides with copper metal: Ullmann reaction.
Redox neutral coupling: the coupling of terminal alkynes with halo-alkynes with a copper(I)
salt in the Cadiot-Chodkiewicz coupling, Thermal coupling of organocopper compounds.
Michael additions to enones where a Grignards would react in a 1,4-addition.
Carbocupration is a nucleophilic addition of organocopper reagents (R-Cu) to acetylene or
terminal alkynes resulting in an alkenylcopper compound (RC=C-Cu). The presence of
magnesium(I) bromide is generally required.

Organocopper reagents: R2CuLi

Preparation:
CH3Li

Two equivalent of lithium compound treated with one equivalent of


cuprous iodide in ether.
+

2 (CH3)3CLi

CuI

ether

CuI.Ph3P

CH3Cu
ether

CH3Li

Li(CH3)2Cu

Li[(CH3)3C]2Cu.PPh3

The aryl, alkenyl and primary alkyl cuprates are prepared by this route but secondary and
tertiary cuprates are obtained from corresponding lithium derivative and ether soluble
derivative of copper (I) iodide such as its complex with tributylphosphine or dimethyl
sulphide.

Properties:
These reagents are more stable and more reactive than the well known Cu(I) reagents.

Structure: The exact composition of the reagent is not well


defined, but the spectroscopic studies and other evidences
shows that in ether it exists in dimer form. The organic
ligands are bonded to tetrahydral cluster of four metal
atoms.

Organocopper reagents: R2CuLi (reactions)


Reaction with organic halide and other homologues reactants:
Nucleophilic substitution bromine or iodine from organic halide by alkyl or alkenyl or aryl
groups at or below room temperature to gives substituted products.
1. n-C6H13-OTs
OH
H3C
H
2.
Br

H
Br

(C4H9)2CuLi

C10H22

ether, -75 C
H3C

3.

Li(CH3)2Cu
o
ether, -15 C

(sec-C4H9)2Cu(cn)Li2
o

Cl

THF, -78 C

I
4.

H3C

Cl

Br

OH
H

) Cu(CN)Li
2 o
2
THF, O C

H
CH3

It reacts with primary alkyl tosylates, with the secondary alkyl halide are not gives product

to high yield by using ordinary organo cuprates such as R2CuLi, these difficulty can be
overcome by using higher order cuprates such as Li2R2Cu(CN) which is prepared from two

equivalent of organo lithium compound and one equivalent of cuprous cyanide.

Organocopper reagents
The important feature of this reagent was that they react with secondary alkyl halide by SN2
mechanism therefore if the starting alkyl halide is optically active then product obtained is
having inversion in configuration.

e.g. Reaction of lithium diphenylcuprate with (-)-(R)-2-bromobutane takes place forming


predominant _______________ of configuration.
C2H5

CH3

Br

(C4H9)2CuLi
ether-THF, reflux

C2H5

CH3

C6H5

But iodide gives a racemic product on reaction with lithium diphenylcuprate which indicates
that the reaction of cuprates with iodides at any rates takes place by a one electron transfer
and not by SN2 reaction.

Alkenyl halide reacts with organocuprates with retensation in configuration of the double
bond to give substituted alkene. The alkenylcuprates react with retensation of geometry of
the double bond.
C6H5

Br
(C2H5)2CuLi

Li(CH3)2Cu
ether, 0oC

C6H5
H

2 HC CH

Organocuprates shows syn-addition to acetylenes


and forming Z-alkenylcuprates.

C2H5

H
CH3

)2 CuLi

I
HMPA
-30 to 25 oC

C2H5
(63%; 95% Z)

Organocopper reagents: R2CuLi (reactions)


Reaction with acid halide and epoxide
Organocuprates are reacts radialy with acid chloride to give ketone and with epoxide to gives
alcohol.

O
R

O
Li(CH3)2Cu
ether, 0 oC

Cl

CH3
C3H7

Addition
elimination
OH

(C3H7)2Cu(CN)Li2
o

THF, O C
86%

Less substituted
carbon atom

Li(CH3)2Cu
OH

ether, -10 C
CH3

Organocopper reagents: R2CuLi (reactions)

Reaction with allylic halides and acetates


Allylic halides and acetates are also react with organocuprates gives either rearranged or
unrearranged product i.e. reaction takes place at the allylic end or the carbon bearing
leaving group.
C4H9
(C4H9)2CuLi

AcO

H9C4

ether, -10 C

(83%)

CO

(17%)

CO

(C4H9)2CuLi
ether, -10 oC

Br

C4H9

(C4H9)2CuLi
O

ether, -30 C

H9C4

COOH

Organocopper reagents: R2CuLi (reactions)


With ,-Unsaturated carbonyl compounds:
The R2CuLi react with ,-unsaturated ketones
-substituted saturated ketone. The
steric hindrance also affects the yield of reaction is increased by using Lewis acid catalyst
such as boron trifluoride etherate and using higher order cuprates Li2R2Cu(CN).
CH3
OMe

OMe

Li(CH3)2Cu
o

ether, -10 C
O

O
H

O
(

n-C4H9

) Cu(CN)Li
2
2
o
ether, -50 C

(n-Bu)2CuLi, BF3
Diethyl ether, -70oC
O

O
53%

Controlling of the stereochemistry of the addition of organocuprates is difficult. It gives


mixture of enantiomers/diastereomers, but one of them is major product formed by approach
of the reagent in a direction orthogonal to the plane of the enone system.

Organocopper reagents: R2CuLi (reactions)


With ,-Unsaturated carbonyl compounds:

Mechanism: The transfer of organo groups from organocuprates to the -position of the
conjugated ketones is uncertain (basically intramolecular).
Most of evidences show that - initial transfer of one electron from organocopper (I) species
to the ketone to give anion radical followed by coupling and intramoleculer transfer of
organic group from the metal to -carbon atom. The R groups of the organocuprate,
R2CuLi, are transfer with retention of configuration which ruled out the formation of free
radicals, therefore R migrates intramoleculerly from cuprate to enone.

R4Cu2Li2

H3CCH=CHCOCH3

H3CCH-CH=CCH3

[R2CuLi]2 +

Cu

(CH3)2CuLi

Br
CH3

CH3

H3C
CH3

R
O-

O
O-

Br
CH3

CH3

Formation of enolate anion confirm by


following example

H+

O-

Cu

R Li R

H3C

CH3

R Li R

CH3

0C
CH3

Organocopper reagents: R2CuLi (reactions)


With ,-Unsaturated carbonyl compounds:
Limitation: Conjugate addition of ordinary organocuprate to ,-unsaturated aldehydes is
not synthetically useful reaction because of the simultaneous formation of products formed by
the reaction at the carbonyl group.
The conjugated addition can be affected by using modified reagent such as Me5Cu3Li2.
Me5Cu3Li2 shows negligible attack on the carbonyl group.
(CH3)5Cu3Li2
CHO Diethyl ether

-CO
CHO
1,4-addition

Organocuprate also shows conjugate cis-addition into ,-acetylenic ester to give ,disubstituted acrylic ester at -78oC. ,-Olefinic esters are not react with organocuprates
under the mild reaction conditions, but conjugate addition can be effected in the presence of
boron trifluoride etherate.
C7H15

COOCH3

C7H15

(CH3)2CuLi
THF, -78oC

H3C
O

R*O
H

CH3

CuI, BF3,
-10oC

R*O

COOCH3

C7H15

H3O+

H3C

Cu
CH3

CH3
Hydrolysis

COOH

COOCH3
H

Organocopper reagents: R2CuLi (Limitations)

Many cases an - excess of reagent has to be required.


Conjugate addition to enones at any rate only one of the two organo-groups in
the cuprates take part in the reaction and other is effectively wasted.
This limitation can be overcome by using higher order organocuprates
R2Cu(CN)Li is that only required in small excess.
The number of other mixed reagents have been developed RrRtCuLi are used in
which Rr is tightly bound to copper and only Rt is transferred.

Organocopper reagents: RCu


Organocopper(I) reagents RCu are less exclusively used in organic synthesis because they
are less stable. The more stable organo compounds as RCuMgBr2 or [RCuBr]MgBr are
used which is formed from equimolar quantity of copper (I) bromide and Grignards reagent
or organocopper in presence of zinc salt. It was added to terminal alkynes to forming
synthetically useful 1-alkenyl copper (I) compound. The R-group and Cu is added to the
same side of double bond.
.RCu.MgBr
2

R'

R'

H
R

. H Cu.MgBr
C
4 9
2

C4H9

C4H9

NH4Cl
OH2

R2CuLi
C4H9

R
H

Cu

H
CH2CH2OH

I2

C4H9

Cu
CO2

O
H
C4H9

R'

CH3I

H
COOH

R
R'

H
H

C4H9

CH3I
NH4Cl
OH2

CH3

C4H9

Organocopper reagents: Castro-Stephens coupling


The Castro-Stephens Coupling is a cross coupling reaction between a Copper(I) acetylide
and an aryl halide forming a disubstituted alkyne.

Example

Organocopper reagents: Ullmann or Ullmann coupling


Ullmann coupling is a coupling reaction between aryl halides with copper or copper-bronze
alloy

The reaction probably involves the formation of an organocopper compound (RCuX) which
reacts with the other aryl reactant in a nucleophilic aromatic substitution.
The Ullmann reaction is limited to electron deficient aryl halides and requires harsh
reaction conditions.
In organic synthesis this reaction is often replaced by palladium coupling reactions such as
the Heck reaction, the Hiyama coupling and the Sonogashira coupling.

Organocopper reagents: Ullmann or Ullmann coupling

Mechanism

Organocopper reagents: Named reactions


The Cadiot-Chodkiewicz coupling is a coupling reaction between a terminal alkyne and a
haloalkyne catalyzed by a copper(I) salt such as copper(I) bromide and an amine base.

Eglinton Reaction

Rosenmund-von Braun Reaction

Sonogashira coupling
Vinyl/aryl halide

Terminal alkynes
The palladium complex activates the organic halides

Complete the following


reactions

7
1. Mg
2. Cu2Br2
3. Alkyne, 4. NH4Cl

3
4

1. Mg
2. Cu2Br2
3. Alkyne

1. Lithiation
2. R2CuLi formation
3. Reaction with RX

Organochromium compounds
The aryl chromium complexes increase the reactivity significantly of the aromatic ring.
E.g. Unsaturated chromium complexes, alkyl chromium species and chromium carbenes.

Synthesis:

Heating the arene with chromium hexacarbonyl, Cr(CO)6.


By ligand exchange (naphthalene) with naphthalene chromium tricarbonyl
complex.
R
R

Cr(CO)6/heat
CO

Structure

3 CO

Cr

CO
CO

Heptacity

The desired arylchromium complex bearing the arene (6-species) and three carbon
monoxide ligands on the chromium (0) atom (18-electron complex).

Reactivity
The chromium atom exerts electron withdrawing effect on the aromatic ring which allows
the nucleohpilic attack on the aromatic ring rather than the electrophilic substitution.
The electron deficient arene ring can stabilized the negative charge, therefore allowing the
metallation (lithium, magnesium, etc) on the ring or at benzylic position.

The chromium can be released easily by mild oxidation such as by using iodine.
The intermediate is converted into cyclohexadiene by protonolysis (by using trifluoroacetic
acid).

Mechanism
The nucleophilic attack on the arylchromium complex can be occurs from the face opposite
to the bulky chromium atom and gives an intermediate 5-cyclohexadiene anion complex.
The nucleophilic attack can be takes place on the carbon atom bearing halogen (ipso
substitution) then subsequent loss of halide anion leads to overall nucleophilic substitution.
COOEt

EtOOC

COOEt

F
EtOOC
CO

COOEt

Cr

CO
CO

Ipso position

CO

COOEt

Cr

CO

CO
CO

Cr

CO
CO

In some cases, the addition of nucleophile to arylchromium complex need not takes place at the ipso
position. Using the hard nucleophile (pKa > 20), the attack is irreversible and forming mixture of the
products from the attack at the ortho-, meta-, and para-positions. Commonly, the attack of the
nucleophile takes place at the meta-position.
The regioselectivity of the substitution can be depends on the nature and location of the substituents
attached to aromatic ring and on the nucleophile.
CH3

CH3
CO

Cr

CO
CO

H3C
Li

S
S

then H+

CH3

S
H3C
CH3

In cyclohexadienyl anion,
hydrogen
shift
and
elimination of HX leads
the overall substitution (not
by ipso substitution).

Addition of reagents such as n- or s-butyllithium to the arylchromium complex normally


results lithiation of the aromatic ring.
O

O
Li

F
nBuLi
CO

Cr

CO
CO

ortho-to fluorine

CO

F
O

Cr

CO
CO

CO

Cr

CO
CO

Nucleophile

Cr(CO)3

Lithiation at benzylic position of arylchromium complexes can be occurs readily using suitable base.
Addition of the electrophile is then takes place at opposite side (less hindered, uncomplexed face) of
the bulky chromium metal.
CH3
Me3Si
MeO

OMe
Cr

nBuLi

Me3Si
MeO
Cr

CH3I

CO COCO

OMe

CO COCO

Hindered
side

Addition of the nucleophile to the chromium complexed benzylic electrophilic carbon or other
electrophilic group occur from the less hindered, uncomplexed faces.
CH3
O

OH

CH3Li

Cr

Cr

CO COCO

CO COCO

Hindered side

Nozaki-Hiyama-Kishi reaction
The addition of CrCl2 to the unsaturated halide (alkenyl or alkynyl) followed by coupling with
aldehyde.
OH
Br +

HOC

CO2Me

CO2Me

CrCl2
THF

The chromium(II) species inserts into the unsaturated halide (or sulfonate) to give the
corresponding organochromium(III) reagent.
The organochromium compounds have low reactivity (basicity or nucleophilic character)
and tolerate (not reacting) many different functional groups, reacting chemoselectively with
aldehyde in presence of ketone or ester.
O

O
+
I

PhCHO

CrCl2
DMF

Ph
OH

This insertion can be catalyzed by nickel salts (NiCl2) or manganese powder. In addition to unsaturated
halides, gem-dihaloalkanes reacts with chromium(II) salts resulting organochromium species which reacts
with aldehyde forming alkenyl halide, which is typically E-selective (alkenylation). This is called as Takai
alkenylation.

Iron Pentacarbonyl [Fe(CO)5]


Reaction of pentacarbonyl iron with sodium amalgam (Na-Hg) forming sodium tetracarbonyl ferrate (II) which is a
volatile reagent. It is used for the synthesis of aldehyde and ketone from alkyl halide.

Fe(CO)5

Na(Hg)

THF

1. Na2Fe(CO)4
RCH2-Br

Na2Fe(CO)4
2. PPh3

3. AcOH

RCH2-CHO

Mechanism:
-

CO

CO

CO
RCH2-Br

+ Na2Fe(CO)4

Na

RCH2

RCH2CO Fe

Fe
CO
CO
R shift
from
Fe to
CO

CO
+

Na

RCH2

Fe
CO
CO

CO
1. PPh3 2 AcOH
.
RCH2-CHO + AcONa + [PPh3]Fe(CO)3

RCH2COOH

OH2

CO

RCH2-CO

RCH2-COX

CO

acid
ROH

R'2NH

RCH2COOR
ester
RCH2CONR'2
amide

The reaction of anion [RCH2Fe(CO)4]- with second molecule of alkyl halide gives
neutral product which after rearrangement undergoes reductive reaction or
rearrangement in presence of suitable coordinating solvent (solvent containing at
least one electron donating atom) forming ketone.
-

CO
CO
+

Na

RCH2

Fe
CO
CO

CO

R'CH2X

CO

RCH2
Fe

R'CH2

CO
CO

solvent

CO

RCH2
Fe

R'CH2CO

CO
CO

R'CH2COCH2R
+
[solvent]Fe(CO)3

Tetracarbonyl Nickel (0) Ni(CO)4


It is important regent for the carbonylation reaction in organic synthesis.
Tetracarbonyl nickel (0) and organo-lithium compound combine to forming unstable
complex which was synthetically important intermediate for the synthesis of aldehyde and
ketone.
-

O
1. R-Li

Li

Ni(CO)4

Ni(CO)3

H+

+
Ni(CO)3

Ni(CO)3

H
solvent

O
2. R-Li

Ni(CO)4

Li

R-CHO

O-

+
R

Ni(CO)3

R'-X
R

Ni(CO)3

Ni(CO)3(Solvent)

Ni(CO)3
R'
solvent

R-CO-R'
Ketone

Ni(CO)3(Solvent)

Olefin undergoes carbonylation reaction by using Ni(CO)4, CO and water in presence of


proton (acid)
Ni(CO)3

Ni(CO)4
+

Ni(CO)3

CO
+
H2O/CO/H

CO
H

+
Ni(CO)3

Ni(CO)2

COOH

Alkynes react with tetracarbonyl nickel (0) in presence of water forming ,-unsaturated
carboxylic acid.
R

+
RCH=CH-Ni(CO)3

H + Ni(CO)4

CO

+
R-CH=CH-CO-NI(CO)3
OH2
R-CH=CH-COOH

The tetracarbonyl nickel (0) reacts with a lithium compound forming an intermediate complex
which shows nucleophilic character of acyl group.
R-Li + Ni(CO)4

O
Ni(CO)3

Ni(CO)3

R-C=O

R
O

O
R

Selenium oxide
(SeO2)
Preparation: It is prepared by heating selenium strongly in air in presence of trace
amount of nitrogen peroxide which acts as catalyst.
Se

O2

Nitrogen peroxide

SeO2

It is also prepared by passing the vapour of sulphuryl fluoride over selenium and silica
contained in a glass vessel
2 SO2F2

Se

SiO2

SeO2

2 SO3

SiF4

Uses: Selenium dioxide is used as oxidizing agent; it oxidized active methyl or methylene
groups as well as allylic group into carbonyl compound without affecting other functional
groups.
i)

CH3CHO + SeO2

ii)

Ph-CO-CH3

iii)

CH3CH2COCH3

+ SeO2
+ SeO2

OHC-CHO
(Glyoxal)
Ph-CO-CHO (Phenyl glyoxal)
CH3COCOCH3 +

CH3CH2COCHO
(major)

iv)

+ SeO2
N

CH3

COOH

(2-Picolinic acid)

When the methylene group is activated by single C=C bond is oxidized into keto-group.
SeO2
O
(Verbenone) (35%)

(2-Pinene)

Mechanism: The oxidation with selenium dioxide is carried out in presence of acetic acid. The
actual reagent taking part in the reaction is a selenious acid. This reaction is proceeds through an
enol ester of selenious acid. The formation of selenious acid ester is the rate determining step.
OH
O
R

H2
C
R'

HO
R

H2 SeO3

R'

SeO2 + OH2 + AcOH

Se

O
R'

O
R

OSe-OH

OH

OH2

R'

R'

enol ester of selenious acid

O
O
R

R
R'
O

H2SeO3
R'
H

O Se
OH

Selenium dioxide in aqueous or alcoholic solution is used in allylic oxidation. During this
oxidation, both allylic alcohols are formed.
HO

H
SeO2 + OH2

or

SeO2 + ROH

HO

The mechanism of this reaction involves selenious acid or equivalent species as a oxidant. The
double bond shows nucleophilic attack on the selenious acid forming unsaturated selenious acid
monoester. The mechanism of this reaction is shows belowHO
HO
O Se
OH

OH
O Se
OH

OH

OSeOH
HO Se
O

If the molecule contain primary, secondary and tertiary hydrogens, the order of oxidation isOH
-CH2- > -CH3 > -CH-.
H3C
CHCH3
CH3CH2

SeO2

H3C
CHCH3
H3C
34%

OH

CHCH3

+
CH3CH2
01%

When double bond is in a ring, oxidation occurs within the ring and at the - to the more
substituted end of the double bond or chain.
CH2CH3

CH2CH3
HO

SeO2

The selenium dioxide is used as dehydrogenating agent. It acts as dehydrogenating agent in


acidic or basic medium. It can be converts ketones into ,-unsaturated ketones, alcohols into
ketone/aldehyde, ester into unsaturated ester. Generally, it dehydrogenates the cyclic ketones, 1,4dicarbonyl systems and primary alcohols
O

O
SeO2

1.

Pyridine

2.
3.

SeO2

CH3COCH2CH2COCH3
EtOOCCH2CH2COOEt

4.

C6H5-CH2OH

5.

C6H5-CH3

SeO2

CH3COCH=CHCOCH3
H

COOEt

170 C
SeO2

at its B.P.
SeO2
at its B.P.

EtOOC

C6H5-CHO
C6H5-CHO

2,3-Dichloro-5,6-dicyano quinone
It is used as strong dehydrogenating agent or strong oxidizing agent. It remove hydrogen
atom from adjacent carbon atom or by rearrangement forming double bond. The reagent
first abstract the hydride ion followed by the removal of proton.
DDQ
0

Benzene/80

Mechanism
Proton shift

H
+
Cl

Cl
O

O
NC

Cl

Cl
OH

Hydride ion
transfer

NC

Cl

CN

CN

OH

O
NC

11. C6H5-CH=CH-CH3

+
DDQ
Ph-CH=CH-CH2
C6H6, reflux

Oxidation allyl methyl/methylene


C6H5-CH=CH-CHO

Cl

CN

DDQ-H
C6H5-CH=CH-CH2-OAr
ArO

C6H5-CH=CH-CH(OAr)2

DDQ
OH2

C6H5-CH=CH-CH(OAr)2