BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 33
Dr. Ajay K. Sah
BITSPilani, Pilani Campus

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How do you avoid the rearrangement problem?

H2SO4
H2O

HO

OH
Hg(OAc)2
H 2O

Oxymercuration

O
Hg

BH4-

O
CH3

CH3

Hg

+ OAc
H

H
O
H

O
H

O
H

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A Hg+2 ion can act like a giant proton

S
LUMO

HOMO

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Demercuration.
O

O
H
H

H 3C

Hg

H3C

HH
O

Hg0

Hg

O
H

O
H

O
H

The Hg+2 is reduced by BH4-.

33

Synthesis of alcohols from alkenes. Oxymercuration

and simple acid catalysis have the same Regiochemistry.
H

1. Hg(OAc)2
2. NaBH4
OH

H
H /H2O

OH

But what if you want the primary alcohol?

How can you reverse
the Regiochemistry?

OH

How do you get the OH group on the primary carbon?

We know that an acid will add to the least
substituted carbon.
A

So if we find an acid that we can add to the alkene

and then convert to a OH- in a second step?

Boron forms lots of 6e- compounds. Lewis acids.

Boron should add to a primary Carbon.

BH3, boron trihydride, has a empty

p orbital and is a good Lewis acid.
H

H
H

S
LUMO

HOMO

BH3 addition to an alkene

H
H

BH2

+ BH3

HH
H

H
H

H3C

hydride shift
H

H3C

H
H

or
H3C

H
H

H3C
First approach,
not very stable

H3C

Sterics is also thought

to be very important, helping
to direct the regiochemistry

H
H

H3C

hydride shift

BH3 addition to an alkene

BH2

+ BH3

H
B
3

OH

H2O2
NaOH

B
tripropylborane
an example of a triakylborane

repeat 2 more times

B
O

O
B

3 NaOH
H2O

OH + Na3BO3

O
B

H2O2

NaOH

OH

Hydroboration

tripropylborane
an example of a triakylborane