LECTURE FOUR

hiral reagents
c
gareth j rowlands
 O

(R)-muscon
e
J. Chem. Soc., Chem., Commun., 1990, 795 & J.
Chem. Soc., Perkin Trans. 1, 1991, 1445 ©baboon™@flickr
 how O

is the selectivity

achieved?

NH
OH N
H
(2 eq.)
MeLi, CuI
O

99% ee
chiral reagent
control

substrate
(achiral)
chiral
reagent
[ ]
substrate
(achiral)

chiral
reagent
chiral
product
 pr o b lem
it is wasteful

©maol@flickr
 H O
B

(+)-α-pinene 9-BBN•THF

of
synthe sis
chiral
H
B
reagent
alpine borane
 O

RL RS

H B O
B H RL

RS

with a
reduction H OH
chiral RL RS
reagent
 O

RL RS

H B O
B H RL

RS

with a
reduction H OH
chiral RL RS
reagent
 O

RL RS

H B O
B H RL

RS

with a
reduction H OH
chiral RL RS
reagent
 (R)-fluoxetin
e
Prozac
J. Org. Chem., 1986, 51, 3394 &
J. Am. Chem. Soc., 1988, 110, 1539

CF3

O H
Me
N
H•HCl

©Touchstone Pictures
 O

Cl
Cl Ipc
B O
H Ph
H
BCl

Cl
2
(+)-Ipc2BCl
H OH

synthesis
CF 3

Cl
using a chiral O H
Me
N

reagent
H•HCl ≥99% ee
1 recrystallisation
 of
synthesis reagent
chiral

pinene
 of
synthesis reagent
chiral

(+)-α-pinene

BH3

H
H 1. TMEDA H
2. BF3•OEt2
B BH2
H H H H
(–)-Ipc2BH (+)-IpcBH2
 of
use boron reagents
chiral
H

H ii. H2O2 H OH
H NaOH
H
H H
B
98.4% ee
H H H
 of
use boron reagents
chiral
Me
Me
ii. H2O2 H
H NaOH
H
HO
BH2 H
66% ee
H
 of
use boron reagents
chiral

i. (–)-Ipc2BOTf
iPr2NEt OH O
O ii. RCHO
R
©Brittany G@flickr
 enolate
geometry

i. (–)-Ipc2BOTf
O iPr2NEt B
O

2
 reagent c hiral
B
O
control
2

H
O
H
OH
R
H
B
O or
H
O OH O
R

R
 OH
O H
O

Me OH O O
H H
O Me

(–)-laulimali
de
fijianolide B
Org. Lett., 2001, 3, 3149

©luxpacis@flickr
chiral reagent control
OH
O H
O

OH O O
H H
O

(+)-Ipc2BO

CO2Me OTBS
H H H
O O O

OH OPMB
CO2Me
H H
OTBS O
H
H O
86%
O OPMB 62%de
organobora
nes ©Pierre J.@flickr
allylation with organoboranes
O
L L
R B
O
RZ
RZ
L R
B RE
RE
L

L L
OH H2O2 B
NaOH O
R
RZ RE R
RZ RE
stereospecific
O
L L
R B
O
RZ
RZ
L R
B RE
RE
L

L L
OH H2O2 B
NaOH O
R
RZ RE R
RZ RE
stereospecific
H L H L
R H
B B
L vs L
RE RE
O O
H R
RZ RZ
stereospecific
H L H L
R H
B B
L vs L
RE RE
O O
H R
RZ RZ
stereospecific
H L H L
R H
B B
L vs L
RE RE
O O
H R
RZ RZ

H
OH H

R RE
OH
RZ RE R
RZ
synthesis
BH3•SMe2 BOMe
MeOH

MgBr K

BF3•OEt2

B B

2 2
chiral reagent control
OH
B O
Et
Et H
2
92% ee
chiral reagent control
OH
B O
Et
Et H
2
92% ee

H H
B OH
Et
H
O
Et
chiral reagent control
CO2iPr OH
O
O
t-Bu
B CO2iPr t-Bu H
O
82% ee
chiral reagent control
CO2iPr OH
O
O
t-Bu
B CO2iPr t-Bu H
O
82% ee
H2O2
NaOH

CO2iPr CO2iPr

O O
H CO2iPr H CO2iPr
B B
O O
O O
t-Bu t-Bu
H H
 OH
O
O O OH
CO2H
O
O
NaO2C
OH O O
O
HO

(+)-SCH351448
Org. Lett., 2005, 7, 3809
©Exothermic@flickr
chiral reagent control O
O O
OH

OH
CO2H
O
O
NaO2C
OH O O
O
HO

OBn O
BnO2C
O H
OBn OH
DCM, 0°C
Ar BnO2C
80% O
N 95% d.e.
Si
N Cl

Ar