Definition:: Inorganic Chemists

Oxidations
Oxidation is one of the most important & useful reactions in

chemistry
Most of the chemicals are obtained by the oxidation of
petrochemicals
Definition:
Inorganic Chemists & Organic Chemists differ in defining oxidation
Inorganic Chemists:
(1) Loss of electrons
(2) Increase in oxidation number
Organic Chemists:
The same rules can not be applied because
(1) Mechanisms of most of the oxidation reactions do
not involve a direct electron transfer
(2) It is also not possible to apply oxidation number
uniformly
1
CH-‐423 Course on Organic Synthesis; Course Instructor: Krishna P. Kaliappan
Oxidations
Addition of oxygen
OH
H3C CH3 H3C C H3C CHO H3C CO2H
H2
Replacement of hydrogen atom bonded to carbon with another,

more electronegative element like oxygen
Elimination of hydrogen
H3C CH3 H2C CH2 HC CH
Simplest Definition
Most oxidations in organic chemistry involve a gain of oxygen
and/or a loss of hydrogen
The reverse is true for reduction
There is no oxidation without a concurrent reduction
2
Oxidations
Oxidation
At single carbon Vicinal Carbon Hetero atom Unfunctionalized

Carbon atom
Reagents
1. Metal based
2. Non-metal based
3
Metal Based Oxidations
Chromium based oxidation
Manganese based oxidation
Ruthenium based oxidation
Osmium based oxidation
Molybdenum based oxidation
Lead based oxidation
Titanium based oxidation
4
Metal Based Oxidations
Chromium based reagents
CrO3
Jones oxidant
PCC
PDC
Collins reagent
Chromyl chloride
Reactivity & selectivity depends on the (1) Solvents & (2) Chromium
ligands
Substantial selectivity can be achieved by choice of the particular
reagent or conditions
The most widely employed transition metal oxidations are Cr(VI)

based reagents
5
Oxidations
CrO3
O
CrO3 + H2O HO Cr O
O
O O O
2 HO Cr O O Cr O Cr O + H2O
O O O
In dilute solution the chromate ion is present. As concentration

increases the dichromate ion dominates
The extent of protonation of these ions depend on the pH
In acetic acid, CrO3 exists as mixed anhydride of acetic acid &

chromic acid
O O O O
OH O
CH3COOH + CrO3 Cr Cr
O O
O O O
6
Oxidations
CrO3
In pyridine, CrO3 exists as an adduct involving Cr-N bond
O
N + CrO3 N Cr O
O
The most common transformation effected on with Cr(VI) is the

convertion of the alcohols into ketones or aldehydes
H
O
CrO3
R OH R O Cr OH R O + H2CrO3
O
A variety of experimental conditions have been used for

oxidation of alcohols by Cr(VI) on a synthetic scale
7
Jones Oxidation
Jones Reagent: Acidic aqueous solution of chromic acid. Generally
added to an acetone solution of the alcohol
CrO3 + H2SO4 + H2O
Use: For simple, unfunctionalized alcohols Jones reagent can be used

OH O
Jones reagent
Acetone
Jones
OH Reagent O
Jones
Reagent
OH O
8
Jones Oxidation
Advantages:
(1) Cr(VI) Cr(III)
Precipitate
Acetone can be decanted. Easy to work up
(2) Good reagent to oxidize primary alcohol to acid
Disadvantages:
(1) Saturated primary alcohols are oxidized to carboxylic acids
Jones reagent O
R OH
Acetone R OH
H
Hydration OH
R O R OH
(2) Not good method for acid sensitive groups & compounds
(3) Under acidic condition dehydration may also take place
9
CrO3. 2Pyridine (Collins reagent)
Preparation:
CrO3 + 2 Pyridine CrO3. 2pyridine
(anh.) (anh.) (Solid)
Uses:
(1) Where other functional groups are susceptible to

oxidation
(2) When the molecule is sensitive to strong acid
(3) Primary & secondary alcohols are oxidized to aldehydes &

ketones in non-aqueous solution (Generally DCM was used)
without over oxidation
(4) Neither markedly basic, nor acidic
10
CrO3. 2Pyridine (Collins reagent)
OH O
CrO3. Py
OH O
Ph CrO3. Py Ph
Ph Ph
O O
CrO3. Py
OH O
The double bond did not migrate
Disadvantages:
(1) Must use a large excess of the reagent
(2) It is moisture sensitive & loses its activity in aqueous solution
11
Pyridinium Chlorochromate (PCC)
Preparation:
O
O
CrO3 Pyridine O Cr Cl
+ 6N HCl HO Cr Cl N
O
O H
Orange-yellow
crystalline solid,
Less hygroscopic
Advantages:
(1) Reagent can be used in stoichiometric amounts with substrate
(2) It is less hygroscopic. So, it can be stored for a long time
(3) PCC is slightly acidic, but can be buffered with NaOAc
12
O PCC O
O CH2Cl2 O OH PCC O
OH O
PCC
Ph Ph
OH O
Oxidation of Organoboranes:
R (1) BH3.THF O
R
R
R (2) PCC, 0oC
Deoximation:
R1 R2 PCC O
N R1 R2
OH
13
Oxidation of tertiary allylic alcohols:
OH
PCC
CH2Cl2
O
O
O Cr O PyH
O O
O Cr O PyH
O
O O
O O
1. MeMgBr, CeCl3 1. MeMgBr, CeCl3
2. PCC, CH2Cl2 2. PCC, CH2Cl2
14
Oxidation of tertiary allylic alcohols:
OH
PCC O
OH
PCC
15
Oxidative cationic cyclization:
PCC
CH2Cl2
OH O
Oxidation
ene reaction
O OH
H
OH O
OH O
PCC PCC
CH2Cl2
16
Oxidation of enol ethers to lactones:
PCC PCC
CH2Cl2 O O
O O O O
R H
R H
R O
OR' OR'
O O O
O Cr OR'
Cr Cl O PyH
Cl O PyH
Oxidation of furan ring system:

O
R H3C
H3C O O R
OH HO
R
H3C H3C
O O
O O OH
Cr O HO
Cl O R
17
Oxidation of active methylene group:
PCC
O O
PCC
O O O
18
Pyridinium Dichromate (PDC)
Preparation:
O O O O
Pyridine
2CrO3 + H2O HO Cr O Cr OH O Cr O Cr O
O O N O O N
H H
Solubility:
Soluble in water, DMF, DMSO, dimethylacetamide. It is
sparingly soluble in dichloromethane
19
Advantages:
(1) Excellent reagent for oxidation of allylic alcohols
(2) There is no over-oxidation of aldehydes
PDC
CHO
OH DCM
(3) No E/Z-isomerization
(4) Unlike conjugated aldehydes non-conjugated aldehydes are
readily oxidized to acids by PDC in DMF at 25oC
HO HO O
PDC
DMF
20
Uses:
PDC
R OH R O
CH2Cl2
R OH PDC R O
CH2Cl2
R' PDC R'
R OH CH2Cl2
R O
OH O
PDC
DCM
O CH2OH PDC
O CHO
DCM
21
PDC PDC O
O CH2Cl2 DMF
OH OH
PCC
CH2Cl2
This reaction is
complicated by the
cationic cyclization
O when PCC was used
22
Miscellaneous Oxidation of CrO3
CrO3/AcOH HO2C
CO2H
H2O
O
CrO3/AcOH
H2O
HO O
H2O O
O OH O O O
Cr
O O OH
O
Cr
O
O
HO2C C
CO2H H2O CO2H
HO3Cr O
O
O O O H O
H2O Cr
O
23
Etard reaction
CHO
CrO2Cl2
CH2Cl2
OR OR
CH3 CHO
CrO3
Ac2O
CrO3
Ac2O
AcO H OAc
C CHO
Hydrolysis
24
Supported Reagents
(1) PCC on alumina
(2) PCC on polyvinylpyridine
H2 H H2 H
C C n C C n
R2CHOH O
Cross link CrO3.HCl
R R
N N N
.
CrO3.HCl
H2 H H2 H
C C n C C
1) Remove CrO3 n
2) HCl wash
3) KOH wash
N N
.
4) H2O wash
Cr(III)
Advantage:
Improved yields due to simplified work up
25
Transformation Chromium reagent
R CHO
PCC, Collins reagent,
R OH
PDC in DCM
OH O PCC, Collins reagent,
R R' R R' PDC, Jones reagent
R COOH
Jones reagent, PDC
R OH
in DMF
CHO
Etard reaction
26
KMnO4 MnO2 Mn(OAc)3
Potassium permanganate (KMnO4)

Under mild condition KMnO4 can effect conversion of alkenes to
glycol
KmnO4 is such a powerful oxidant that it can cleave the glycol
further. So, careful control is required
R' R' O O R' OH

HO O
+ KMnO4 Mn + Mn
R R O O-K+ R OH HO O-K+
R' O O R' OH R' O

Mn
R O O-K+ R O R O
H
27
In water medium:
KMnO4, H2O R O
R R'
O R'
R R' R R'
HO OH O OH
KMnO4, H2O
Ar ArCO2H
KMnO4, H2O
Ar CH3 ArCO2H
28
In Organic Solvents:
3.3 mol KMnO4
Benzene polyether OH O
1.0 mol KMnO4 OH O

R4NCl
Oxidation of acetylenes:
KMnO4 Ph CH2CH2CH3 Ph CH2CH2CH3
Ph CH2CH2CH3
R4N+, DCM HO OH O OH
Ph CH2CH2CH3
O O
29
Oxidation of aromatic side chain:

KMnO4
Ar R Ar CO2H
Oxidation of amino compounds:

KMnO4
R3C NH2 R3C NO2
Tertiary alkylamines can be oxidized to nitro compounds
Oxidation of sulphides:
NO2 NO2
O
KMnO4
O2N O2N S
S
O
30
Oxidation of terminal alkynes:
KMnO4
CO2H
Application in the synthesis of Saccharin:

Me (NH4)2CO3 Me
SO2Cl SO2NH2
O
KMnO4 CO2 Na
NH
OH- SO2NH2 S
O2
Saccharin
31
Manganese dioxide (MnO2)
Uses:
Selective oxidation of allylic & benzylic alcohols
OH O
MnO2 Excess of MnO2
CH2Cl2 is required
OH OH
MnO2, KCN
CN
EtOH
O
O
EtOH
CN
OEt
32
MnO2
ROH
OH
CO2R
NaCN
MnO2
OH H CN
O CN OH
MnO2
OR R OH CN
O O
33
CH2OH CHO
MnO2 MnO2
OH
CHO
DCM
HO O
OH MnO2 MnO2, CH2Cl2

CHO
OH OH
OH OH OH OH
MnO2
CHCl3
HO O
34
Manganese(lll) acetate Mn(OAc)3
O O
Mn(OAc)3 OAc
Mn(OAc)2
O OH O O O
Mn(OAc)3 Mn(OAc)3
Mn(OAc)2
Mn(OAc)2
O
OAc
O O
Mn(OAc)3 AcO
35
Manganese(lll) acetate Mn(OAc)3
OH O
Mn(OAc)3
OH
N O N O
Me Me
O OH O OH
Mn(OAc)3
N O N O
Me Mn(OAc)2 Me
OH
OH OH O
N O N O
Me Me
36
Silver-based oxidation
Ag2O
Mild oxidant to oxidize aldehyde to carboxylic acid
O O
Ag2O
+ 2 Ag
R H R OH
CHO Ag O CO2H
2
NaOH
Ag2CO3 on Celite (Fetizon’s reagent)

Conversion of diols to lactones
O
Fetizon's
OH reagent
OH O
O OH Fetizon's O O
reagent
OH OH
37
Ag2CO3 on Celite (Fetizon’s reagent)
Highly selective:
Fetizon's
reagent
OH OH OH OH O OH
Mono-oxidation:
OH O
Fetizon's Fetizon's
reagent reagent
OH OH O OH
OH OH
Mechanism:
R R
R R H
H O H
O H O
Ag Ag+ H2O + CO2 + 2Ag
R R
Ag+ -O O- Ag+ O O
O O
38
Silver acetate
R R I
R I2 O
I
Ag(OAc)2 or R' R' O CH3
R' Ag(O2CPh)2
R OAc R O R O
-OAc
CH3 CH3
R' OAc R' O R' O
H2O
In absence of water, Prevost
Hydroxylation, trans-product
R OH R OH
In presence of water,
Woodwards hydroxylation,
R' OH R' OH
trans product
cis-product cis product
39
Other metal-based oxidation
Hunsdiecker Reaction:
Br2
CO2Ag Br
RCOOAg X2 RCOOX AgX

∇
RCOOX RCOO X (Initiation)
RCOO R CO2
R RCOOX RX RCOO (Propagation)
40
Ruthenium & Osmium tetroxide Oxidation
Mechanism seems to be same in both cases
MO4 O O Hydrolysis OH HO O
M M
O O OH HO O
Reoxidation
O
O
M
O
O
Uses:
Alkenes are generally oxidized to cis-diols
Alkynes are oxidized to diketones as in case of KMnO4
41
Osmium tetraoxide (OsO4)
R
OsO4
R OH OsO4 is highly toxic, cannot
be used at industrial scale
R' R' OH
Syn O
Use of NMO as co-oxidant along with catalytic amount NMO

of OsO4 can be used for higher scale N
O
Selectivity:
Directed by hydroxyl group
OsO4 HO OH OH
NMO HO OsO4
O O HO
HO Pyridine HO HO
OsO4 HO
NMO HO
O O
TMSO Pyridine TMSO
42
Ruthenium tetroxide (RuO4)
Prepared in-situ by mixing RuCl3, NaIO4, CH3CN, CCl4, H2O
Primary Alcohols:
H RuO4
H
H H
OH CO2H
O O
Secondary Alcohols:
Secondary alcohols oxidized to ketones
HO O
RuCl3, NaIO4
CCl4, H2O, CH3CN

O O
O O
Diols:
Diols are further oxidized to carboxylic acids
OH O
RuO4, NaIO4
Ph OH Ph
OH
CCl4, H2O, CH3CN
43
Ruthenium tetroxide (RuO4)
Oxidation of Ethers:
RuO4
O O O
OAc OAc
AcO
OAc O
O O
RuO4
O
RuCl3
OMe OMe
CCl4
MeCN
Oxidation of Phenyl Groups:

RuCl3, NaIO4
R R CO2H
CCl4, H2O, CH3CN
44
Tetra-n-propylammonium perruthenate (TPAP)
A catalytic amount of TPAP with NMO as the co-oxidant oxidizes
a range of functional groups
The performance of this reagent is improved by the addition of MS
TPAP
OHC
HO NMO
O O
OTBDPS DCM OTBDPS
TPAP
NMO
CHO
THPO OH THPO
DCM
45
Tetra-n-propylammonium perruthenate (TPAP)
Groups tolerant are:
Alkenes
THP ethers
Epoxides
Lactones
Silyl ethers
Indoles
46
Lead tetraacetate, LTA ,Pb(OAc)4
Lead tetraacetate is a very good reagent for glycol
cleavage
Particularly LTA is useful for glycols that have low

solubility in aqueous media
OH
Pb(OAc)4
O
O
O O
OH
Carboxylic acids are oxidized by LTA

CO2H
LTA
CHCl3
47
Pb(OAc)4 + RCO2H RCOO-Pb(OAc)3 + CH3COOH
RCOO-Pb(OAc)3 R + CO2 + Pb(OAc)3
R + Pb(OAc)3 R+ + Pb(OAc)2 + CH3COO-
The reductive step is promoted by hydrogen donor

solvents
Acetate arise by the capture of an acetate ion
In presence of lithium chloride, the product is the

corresponding chloride
Cl Cl
Cl CO2H Pb(OAc)4 Cl Cl
H3C CH2CO2Me LiCl H3C CH2CO2Me
48
α- hydroxy carboxylic acids undergo oxidative decarboxylation to
give ketone
O H O H O
+ CO2 + Pb(OAc)2 + CH3CO2H
OH O Pb(OAc)
3
O O
γ- keto carboxylic acid preferentially yield α,β– unsaturated

ketone
HO2C
Pb(OAc)4
Cu(OAc)2
O O
Presumably it goes via oxidation of carboxylic acid to the carbocation

followed by deprotonation
O
H O Pb(OAc)3
49
O O O
OAc OAc
LTA, AcOH
LTA is toxic in nature
OH O O
Pb(OAc)3 AcO
Pb(OAc)4 +
+ + +
AcOH AcOH Pb(OAc)2
O O
LTA
Pb(OAc)3 + AcOH
R OH R O
R+ + AcO- + Pb(OAc)2 CO2 + Pb(OAc)3 + R
R OAc
50
O
O O Pb(OAc)4 O
O Pyridine O
O O
O R R O
H O C O Pb(OAc)3 CO2 + Alkene + Pb(OAc)2 + CH3CO2H
R R
O O Pb(OAc)3
CO2H
H + Pb(OAc)2
+ CO2 + AcOH
O O O
51
O
CO2H
LTA O Pb(OAc)3
+ 2CO2 + Pb(OAc)2
O
CO2H H + AcOH
O
O H O H
LTA O
OH O Pb(OAc)3
O O
52
Oxymercuration
Addition of water to an alkene
Hg(OAc)2 Hg2+ Hg2+ Mercurinium

R R ion
R
When water is used as solvent, it opens the mercurinium

ion and give alcohols
Hg(OAc)2 OH NaBH4 OH
HgOAc
R R R CH3
H2O
C-Hg bond is very weak and it can be easily replaced with

hydrogen by reducing agents. Generally NaBH4 is used
53
Oxymercuration
Addition of water to an alkyne
R
Hg(OAc)2 Hg2+ H2O
R HgOAc
HO
R
This is what we should have expected. But what we get is a ketone

R R
HgOAc Isomerizes to HgOAc
HO O
Since AcOH is the byproduct, this protonates the carbonyl group

R R R
HgOAc
O HO O CH3
H
For hydration of alkynes, we do not need NaBH4. Moreover, if you
use NaBH4 in the last step, it will reduce the ketone
54
Oxymercuration
Hg(OAc)2 O NaBH4 O
OH OH
Hg
AcO AcOHg
O OH O OH
OH OH O
Hg(OAc)2
H2O
OMe O OH OMe O OH
Deoxydaunomycinone
OH OH
Hg(OAc)2 -H2O
H2SO4
O O
55
Wacker Oxidation
O2, HCl
CuCl2 PdCl2 R
Pd0 + HCl
PdIICl
HPdIICl
R
O HO H
H2O
R β- elimination
PdIICl
R
HO
O
O HO HO
Wacker
MgBr oxidation
56
Molybdenum Peroxy Complexes:
MoOPH (MoO5. Py. HMPA complex)
It contains two electrophilic bridged peroxy ligands and a single oxo-

unit + O O O
Li
O O Mo
LDA O
O
R R L L'
R' R'
L= HMPA
L'= Pyridine
O O
O O
O
R Mo O OH
R
R'
L L' O R'
H OH
O O
LDA
CH3 CH3
O MoOPH O
O O
57
Elimination reactions
N
O Cope elimination
H
O O O Ph O
SePh Se
LDA 1 eq. NaIO4 O
PhSeSePh
H
OAc
SMe
OH O S
CS2, MeI
58
Non-Metal based oxidation
Activated Dimethyl sulfoxide (DMSO)
H R
E R2CHOH R O
S O + E+ S O S O Me2S
R R
Electrophiles Nucleophiles
SOCl2, (COCl)2, Cl2, ROH, PhOH, PhNH2,
TsCl, (CH3CO)2O, R2C=N-OH, Enols
SO3/pyridine, CF3SO3H
Swern Oxidation
Moffatt Oxidation Most of these
reactions take place at
Kornblum Oxidation very low temperature
Corey-Kim oxidation
DMSO-Ac20
59
Swern Oxidation
Cl
Cl
S O -CO2, -CO
O
S O + O
O
O -Cl-
Cl
Cl
-HCl S O O
S Cl R
R
H H
OH Et3N
R
O O
Cl
DMSO, (COCl)2
CH2Cl2, Et3N
OH O
Trifluoroacetic anhydride also can be used instead of (COCl)2
60
Swern Oxidation
Survives protecting groups
CH(OEt)2 CH(OEt)2
Swern
Oxidation
OH O
O O
O O
No epimerization of aldehydes
CH3 CH3
H Swern H
Oxidation
OH CHO
Swern H
Oxidation
OH O
61
Moffatt Oxidation
R
O
H R
RHN
S O R N C N R NR
S O
R
O
R
O R
O R
Me2S
R R S H
Base
O O
O O DMSO O O DMSO
OH O
DCC CO2Me DCC CO2Me
O O
OAc OH OAc O S S
62
DMSO, Ac2O
R
R' R
-OAc- -OAc- + Me2S
S O + Ac2O S OAc H O
S O + AcOH
R'
OAc
OH
R R'
Disadvantage: Alcohol may attack acetate
DMSO- SO3- Py
O O RCH2OH R
Py
N S O S O S RCHO + Me2S
S H O
O S O O
O
OH OH
DMSO
OH SO3, Py
O
63
Kornblum Oxidation
Oxidation of alkyl halides to aldehydes
O
S R NaHCO3
RCH2Br S RCHO + Me2S
H O
Base
Corey-Kim Oxidation
O
R
R
S Cl N S Cl S
H O
O R
HO Base
R
R2CO + Me2S
64
Tetramethylpiperidine nitroxide(TEMPO)
OH R O
N O HO N N OH
O R H
R
H
It is a stable NaOCl
nitroxide and is TEMPO can be
the active reagent used in catalytic
in oxidizing amount if NaOCl
N O
alcohols or NCS is used in
stoichiometric
amount
TEMPO
(2 mol%)
PhCH2O(CH2)2CH2 OH PhCH2O(CH2)2 CHO
NaOCl
65
Tetramethylpiperidine nitroxide(TEMPO)
This reagent can selectively oxidize primary alcohols in the
presence of secondary alcohols
TEMPO
(10 mol%)
CH3CH(CH)8CH2 OH CH3CH(CH)8CHO
OH NCS(1.5 eq)
OH
TBACl
It can also oxidize primary alcohols to carboxylic acids by a

subsequent oxidation with hypochlorite ion
TEMPO
RCH2OH RCOOH
NaOCl (3 eq)
TBACl
CHO
OH
N N
CO2tBu CO2tBu
66
Epoxidation
O
O H
Nu O
O R OH
R O Nu
R = EWG
Stabilized
Electron rich substrate and electrophilic reagent
electron rich
Electron deficient substrate and nucleophilic reagent
O
electron deficient
67
Epoxidation
Electrophilic reagents
1. Peracetic acid
2. Perbenzoic acid
3. m-CPBA
4. KHSO5 (Oxone)
5. Dimethyldioxirane (DMDO)
Peracids
Peracids can be prepared from the corresponding acids & H2O2
RCO2H + H2O2 RCO3H + H2O
68
Peracids
Mechanism: O R
H O O
O R R
+ RCOOH
R R R R
R R
It is believed to be a concerted process
Stereospecific syn addition is constantly observed
Epoxides are always syn. Trans epoxide means substituents are trans
The rate of epoxidation
The reactivity of the peracid is increased by EWG’s

Strong EWG attached to olefin makes it less reactive
CF3CO3H O
CO2Me CO2Me
69
Peracids
Stereoselectivity:
R' m-CPBA H O R' m-CPBA H O H
R H R R' R R'
R
Addition of oxygen comes preferentially from the less hindered
side of the molecule
O
H
H H m-CPBA O
+
H
2 : 1
H H
m-CPBA
O
H H
Regioselectivity:
m-CPBA
O
More electron rich double bond participated in epoxidation

70
Peracids
Henbest epoxidation:
Epoxidation directed by a polar group
Hydrogen bonding between hydroxyl group & the reagent stabilizes
the transition states
R
OH OH
O
H
m-CPBA H O
O H O
O
H
OAc OAc OAc
m-CPBA
O + O
(57:43)
NHAc NHAc
m-CPBA
O
71
Peracids
Henbest epoxidation:
CO2Me CO2Me
m-CPBA
OH OH
O
HO H HO H
m-CPBA
O O
O
H H
RO H RO H
m-CPBA
O O
O
H H
O O H
H
KOH
O O
H2O2 O
H H
72
Peracids
Rubottom Oxidation:
O OTMS O
TMSO
O OH
m-CPBA
OAc O O
AcO O
O O
H+ OAc
Epoxides derived from vinyl silanes are converted into aldehydes

or ketones under mild acidic condition
O H+, H2O
TMS R R2CHO
H R
73
Can you do epoxidation in non-acidic medium? Yes
Nitrile & H2O2

NH H
R C N + H2O2 Peroximidic
O
R O acid
R R
O
R R R
O R By product is
R R R NH2 amide, not acid
DCC-H2O2
H2O2 N R
H O
N C N N C DCU
MeOH R (neutral)
O H
O
Looks like peracid
74
Methyltrioxorhenium (MeReO3)
Ph Ph
MeReO3
O
Py, CH2Cl2
30% H2O2
Dioxiranes (Murray’s reagent)

KHSO5
(Oxone) O
O
O
Dimethyldioxirane (DMDO)
F3C H2O2 F3C

O More reactive analogue
O
F3C F3C
O of DMDO
Uses:
Epoxidation of olefins
Oxidizes sulfides to sulfoxides & sulfones
Oxidation of amines to amino N-oxides
Oxidation of aldehydes to carboxylates
75
Dioxiranes (Murray’s reagent)
Mechanism:
O
O O
C12H25
N O , KHSO5
N,N-Dialkylpiperidin-4-one salts are
H3C also good catalysts for epoxidation
The quarternary nitrogen enhances the reactivity of the ketone

towards nucleophilic addition
F
OH H3C KHSO5 O OH
O
H3C K2CO3
Ph Ph
F 93%
89% ee
76
Epoxidation of electrophilic alkenes
O O
H2O2
O
NaOH
O O O
O
O O
H
O O
O H
O O O
H2O2/NaOH m-CPBA
O O
CF3CO2H
R OMe R OMe
O
H2O2/NaOH cannot be used as ester will get hydrolyzed and
m-CPBA is unreactive
77
Baeyer- Villiger oxidation
H
O O O
R'CO3H
O R' + R'COOH
R R R O R OR
R
O
O H O O
O
O O CO2H
CO3H
O
CH3CO3H
O O
O
O
O
O
CF3CO3H
78
Transformation of epoxides
Nu
R Nu R
O OH
O
R BF3.Et2O O BF3 O BF3
R R
O H R H
H2O2 OH
HCO2H
OH
O H2SO4 H3C OH
H3C H3C
H3C CH3 MeOH MeO CH3
79
Transformation of epoxides
Base catalyzed ring opening of epoxides leads to allylic
alcohols O
Base HO
LDA
LiClO4, CF3SO3Li, Mg(ClO4)2, Zn(OTf)2, Yb(OTf)3 catalyze the

epoxide ring opening.
OH
O
NR2
R2NH
LAH acts as a nucleophilic agent & attacks at the less
substituted carbon atom of the epoxide ring. DIBAL-H also
serves the purpose
OH
O LAH
R CH3
R
80
Oxidation with Singlet Oxygen
Generation of singlet oxygen:
Photosensitizer + hν 1
[Photosensitizer]*
1 3
[Photosensitizer]* [Photosensitizer]*
3 3 1
[Photosensitizer]* + O2 Photosensitizer + O2
H2O2 + -OCl 1O + H2O + Cl-

2
O
(RO)3P + O3 (RO)3P O (RO)3P=O + 1O
2
O
Ph Ph
O O
1O
2
Ph Ph
81
Mechanism:
1. Concerted mechanism
O OH
O H O
2. Perepoxide-intermediate mechanism
O O
OH
O H O H O
There is a preference for removal of a hydrogen from

more congested side of the double bond
82
O
(PhO)3P O -OCl
O
O OH O OH
-35 oC H2O2
O
O
OCH3
1O O O O OH
2 MeOH
OCH3
OCH3 OCH3
OCH3
CH3CHO
O O
CH3
O
OCH3
83
SeO2 Oxidation
H 1. SeO2 OH
R 2. H2O2 R
Mechanism:
R'
OH HO O R'
O H R' H OH
Se O Se
Se O Se
O R R R'
R H R
R'
O Cat. SeO2
SeO2 t-BuOOH
Se
HO O R'
R
HO R'
84
SeO2 Oxidation
OAc 1. SeO2 OAc
2. NaBH4
HO
PhSeCl Oxidation
O O O Ph O
1. LDA SePh Se
H2O2
O + PhSeOH
2. PhSeCl H
Phenyl Sulfoxide Oxidation

O O O Ph O
1. LDA SPh S
m-CPBA O Δ
2. Ph-S-S-Ph
85
NaIO4 Oxidation
R R
R R IO4 -
2 RCHO + H2O + IO3-
O O
HO OH I
O O
HO OH
HO O OH
O O O O O
OH- I
IO4- O I O
O
O O O O
OH
H2O
OH
O OH
2 CH3COOH + IO3- + H2O I O
O O
OH OH
86
Ozonolysis
O O
O3
R R' +
R H R' H
O Retro R
O O O O
[3+2] O O [3+2] O O O
+ + O
R R O
R R R
R R
[3+2]
O R
Me2S O
2 RCHO + Me2S=O
O
R
PPh3 Ph3P=O
Zn ZnO
NaBH4
Ozonide RCH2OH
EtOH
87
Ozonolysis
MeO
OMe
will undergo ozonolysis

faster than other
Reductive workup:
1. O3
2. Na2SO3 O
N N
Oxidative workup:
O
1. O3, HCOOH HO2C CO2H
O
2. H2O2 HO2C CO2H
88
Oxidation with N-sulfonyloxaziridines
O 1. KHMDS O
2. O
NSO2Ph OH
Ph
NSO2
NSO2
HO R
O O
H R H R H
R O R O
R O
PhCH2OCH2O PhCH2OCH2O OH
1. KHMDS
CH2CO2Me
Me2HC 2. O Me2HC CO2Me
Me NSO2Ph Me
Ph
89
Oxidation of Unfunctionalized carbon
Barton reaction:
H
NO
OH NOCl O hν O
Py
NOH NO
OH OH OH
NO
O
OH
90

Definition:: Inorganic Chemists

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Definition:: Inorganic Chemists

Uploaded by

Copyright:

Available Formats

Oxidations

Oxidation is one of the most important & useful reactions in

Replacement of hydrogen atom bonded to carbon with another,

The reverse is true for reduction

There is no oxidation without a concurrent reduction

At single carbon Vicinal Carbon Hetero atom Unfunctionalized

Chromium based oxidation

Manganese based oxidation

Ruthenium based oxidation

Osmium based oxidation

Molybdenum based oxidation

Lead based oxidation

Titanium based oxidation

The most widely employed transition metal oxidations are Cr(VI)

In dilute solution the chromate ion is present. As concentration

The extent of protonation of these ions depend on the pH

In acetic acid, CrO3 exists as mixed anhydride of acetic acid &

The most common transformation effected on with Cr(VI) is the

A variety of experimental conditions have been used for

Use: For simple, unfunctionalized alcohols Jones reagent can be used

(1) Where other functional groups are susceptible to

(3) Primary & secondary alcohols are oxidized to aldehydes &

(4) Neither markedly basic, nor acidic

(1) Reagent can be used in stoichiometric amounts with substrate

(2) It is less hygroscopic. So, it can be stored for a long time

(3) PCC is slightly acidic, but can be buffered with NaOAc

Oxidation of furan ring system:

Oxidation of active methylene group:

R' PDC R'

Transformation Chromium reagent

Potassium permanganate (KMnO4)

R' R' O O R' OH

R' O O R' OH R' O

1.0 mol KMnO4 OH O

Oxidation of aromatic side chain:

Oxidation of amino compounds:

Tertiary alkylamines can be oxidized to nitro compounds

Application in the synthesis of Saccharin:

OH MnO2 MnO2, CH2Cl2

Ag2CO3 on Celite (Fetizon’s reagent)

RCOOAg X2 RCOOX AgX

R RCOOX RX RCOO (Propagation)

Alkenes are generally oxidized to cis-diols

Alkynes are oxidized to diketones as in case of KMnO4

Use of NMO as co-oxidant along with catalytic amount NMO

CCl4, H2O, CH3CN

Oxidation of Phenyl Groups:

The performance of this reagent is improved by the addition of MS

Groups tolerant are:

Particularly LTA is useful for glycols that have low

Carboxylic acids are oxidized by LTA

Pb(OAc)4 + RCO2H RCOO-Pb(OAc)3 + CH3COOH

RCOO-Pb(OAc)3 R + CO2 + Pb(OAc)3

R + Pb(OAc)3 R+ + Pb(OAc)2 + CH3COO-

The reductive step is promoted by hydrogen donor

Acetate arise by the capture of an acetate ion

In presence of lithium chloride, the product is the

γ- keto carboxylic acid preferentially yield α,β– unsaturated

Presumably it goes via oxidation of carboxylic acid to the carbocation

LTA is toxic in nature

R+ + AcO- + Pb(OAc)2 CO2 + Pb(OAc)3 + R

Hg(OAc)2 Hg2+ Hg2+ Mercurinium

When water is used as solvent, it opens the mercurinium