METHODS FOR THE SYNTHESIS OF ALCOHOLS (to date)

-
I OH OH

1. BH3 OH
OH H+/H2O
2. NaOH/H2O2

OH OH
1. OsO4 1. mCPBA
OH
2. H2O2 2. H+/H2O OH
SYN ANTI

O
Aldehydes
OH
R H
H
R
O
Ketones OH
Na
R R
R
R
O epoxides

R OH
R
 ELECTROPHILIC AND NUCLEOPHIC CARBON
Methylmagnesium bromide Methyl lithium Methyl chloride

d- d+ d- d+ d+ d-
H3 C Mg Br H3 C Li H3C Cl
 TYPICAL ELECTROPHILES
Methyl chloride
O d-
d- acetone
d+ d+
H3C Cl
Alcohols, carbonyl compounds and carboxylic acids:
REDUCTION
Reduction: Addition of H2 (or H-), loss of O or O2 ; loss of X2

O O
H H NaBH4 LiAlH4
R C H R C OH R C R C
or
Raney Ni/ H OH
H H
Primary alcohol H2 Aldehyde Carboxylic acid

must convert OH to
leaving group
O
H H NaBH4
R C H R C OH R C
or
Raney Ni/ R'
R' R'
H2 Ketone
Secondary alcohol

must convert OH to
leaving group
H H
R" R" Li H Al H Na
H B H
R C H R C OH
H H
R' R' Lithium aluminium Sodium borohydride
hydride
Tertiary alcohol
 Comparison of
Reducing Agents
• LiAlH4 is stronger.
• LiAlH4 reduces more
stable compounds
which are resistant to
reduction.
=>
Alcohols, carbonyl compounds and carboxylic acids:
OXIDATION
Oxidation: loss of H2 , addition of O or O2, addition of X2 (halogens)

O O
H H PCC Na2Cr2O7 /
R C H R C OH R C R C
H H2 SO4 OH
H H
Primary alcohol Aldehyde Carboxylic acid

O
H H Na2Cr2O7 /
R C H R C OH R C X
H2 SO4 R'
R' R'
Secondary alcohol Ketone

PCC
R" R"
NH CrO3Cl-
R C H R C OH X

R' R'
Tertiary alcohol