Download Oxidation Reactions

CHM 422 Organic Synthesis, Dr. Laurie S. Starkey
Common Oxidation Reactions
primary alcohols (1˚ ROH)
OH
R
R
Swern
H
H
O
PCC or
PCC
N H CrO3Cl
H
O
Jones
R
pyridinium chlorochromate
(CrO3-py-HCl)
OH
secondary alcohols (2˚ ROH)
OH
R
R
Swern (2 steps)
O
PCC or
1.
Swern or
Jones
H
R
R
[ox]
tertiary alcohols (3˚ ROH)
no reaction
benzylic carbons (if R is not a quaternary carbon)
R
CO2H
Jones
R
H
alkynes
R
R
H
1. O3
O
R
2. Zn or DMS
R
ozonolysis, followed by reductive workup
DMS: dimethylsulfide
O
2
2. H2O
R
R
OOH
cis dihydroxylation (use H2O2/H3O+ for anti
dihydroxylation, via epoxide ring opening)
R
O
Cl
mCPBA:
m-chloroperoxybenzoic acid
OH
R
OsO4
R
R
HO
1. O3
R
oxalyl chloride
2. (CH3CH2)3N (Et3N, triethylamine)
epoxidation
(ROOR)
R
Cl
O
mCPBA
R
Cl
dimethyl sulfoxide
(DMSO)
O
KMnO4 or
CH3
CrO3, H2SO4 or Na2Cr2O7, H2SO4
alkenes
R
O
O
Jones (chromic acid)
or KMnO4
R
CH3
O
S
OH
H
CH3
H3O+
HgSO4
hydration (via enol)
S
CH3
O
R
CH3
O
ketones
O
mCPBA
(RCO3H)
O
Baeyer-Villiger reaction
migratory aptitude: hydrogen > 3˚ alkyl >
2˚ alkyl > phenyl > 1˚ alkyl > methyl