SELECTIVITY

SELECTIVITY
Science 1983, 219, 245
Chemoselectivity
preferential reactivity of one functional group (FG) over another
- Chemoselective reduction of C=C over C=O:
H2,
Pd/C

- Chemoselective reduction of C=O over C=C:

O

OH

NaBH4

NaBH4, CeCl3

OH
only

- Epoxidation:
MCPBA

+
OH

OH

O
(2 : 1)

VO(acac)2,
tBuOOH
OH

OH

exclusively

Regioselectivity
- Hydration of C=C:
1) B2H6
2) H2O2, NaOH

OH

OH
R
1) Hg(OAc)2, H2O
2) NaBH4

- Friedel-Crafts Reaction:
O
RCOCl,
AlCl3

R
O

O
SiMe3

RCOCl,
AlCl3

OH

SELECTIVITY
- Diels-Alder Reaction:
R

+
O
major
O

minor
O

O
minor

major
O

+
O

OAc

OAc

OAc

OAc

OAc

Raney Ni, H2

+
O

SPh

SPh

Change in mechanism:
SPh
PhSH, H+
R

SPh

PhSH, (PhCO2)2

Stereochemistry:
Relative stereochemistry: Stereochemical relationship between two or more stereogenic centers
within a molecule

HO
cholesterol

H
enantiomers
same relative stereochemistry

H
OH

syn: on the same side ( cis)

anti: on the opposite side (trans)
- differences in relative stereochemistry lead to diastereomers.
Diastereomers= stereoisomers which are not mirror images; usually have different physical
properties

SELECTIVITY
Absolute Stereochemistry: Absolute stereochemical assignment of each stereocenter (R vs S)
Cahn-Ingold-Prelog Convention (sequence rules)
- differences in absolute stereochemistry (of all stereocenters within the molecule) leads to
enantiomers.
- Reactions can "create" stereocenters
O
Ph

MeMgBr

HO

Ph

MeMgBr

CH3
H

H 3C

OH

Ph

enantiomers
(racemic product)

Ph
H
HO

CH3

Ph

MeMgBr

Diastereomeric transition states- not necessarily equal in energy

Me

Me

Me

Ph

Zn

CH3 CH3
Zn

Me
N

O
CH3 CH3

Zn

H 3C

Zn
Ph

H 3C

HO
Ph

CH3

HO

CH3

Ph

Diastereoselectivity
CH3MgBr
Ph

CH3

Ph

CHO

HO

CH3

Ph

H OH
anti

syn

Diastereomers

Cram Model (Cram's Rule): empirical

O
O
M
S

H 3C
Nu

CH3MgBr

CH3MgBr

L
R

favored

H
Ph

SELECTIVITY

Felkin-Ahn Model
S O

O M
L

Nu

Nu

M R

disfavored

favored

Chelation Control Mode

M
OR
O

O
R
S

HO

OR

CH3MgBr

CH3MgBr

favored

Nu

OR

HO
TBSO

TBSO

MgBr

relative stereochemical control

H O

H O

OBn

OBn

Stereospecific
Stereochemictry of the product is related to the reactant in a mechanistically defined manner; no
other stereochemical outcome is mechanistically possible.
i.e.; SN2 reaction- inversion of configuration is required
Br2

H 3C

Br

Br2

meso

H
CH3

Br

CH3 Br

H
CH3

Br

CH3
H

Br
H

CH3 Br

enantiomers (racemic)

Stereoselective
When more than one stereochemical outcome is possible, but one is formed in excess (even if that
excess is 100:0).
CH3

H2, Pd/C

H
H
-pinene
O

only isomer
O

CH3
H
not observed
O

LDA, CH3I
N

O
S

O
S

(96 : 4)
Diasteromers

Diastereoselective
Enantiospecific