Page 777 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 8.15. Synthesis of Ketones, Esters, Carboxylic Acids, and Amides by Palladium- 753
Catalyzed Carbonylation and Acylation
SECTION 8.2
A. Ketones by carbonylation
Reactions Involving
1 a Pd(PPh ) Cl , 2 O Organopalladium
3 2
3 mol % Intermediates
Br I + (HO) B Br C
2
CO, K CO 3 86%
2
2 b O
PhCH PdCl/PPh 3
2
I + (n-Bu) SnCH CH CCH CH
3 2 2
CO, 50°C
93%
O
3 c Sn(CH ) CCH CH C(CH )
3 3
PhCH PdCl/PPh 2 3 2
) C Cl + 2 3
(CH 3 2 CHCH 2
O CO O 75%
4 d
I
CH OTIPS O
CH + 2 CH 2 OTIPS
3 Pd (dba) , 2.5 mol %
N N 2 3
(CH ) Sn Ph As, 2.2 mol %
N O 3 3 CH 3 CH 3
3 CH
CO, LiCl, THF N N 3
CH 3
N O
B. Esters, acids and amides
CH
5 e 3
85%
Pd(PPh ) (OAc) ,
Ph O SCF 3 2 2 Ph H
3 3 CO 2
CO, NaOAc 82%
6 f O
O Pd(OAc) ,
2
dppp
CO CH O C
SO 3 2 86%
CF 3 3 CH 3 OH
O
O CH
7 g CH 3 Pd(OAc) , 8 mol % CH 3
2
CH 3 PPh , 16 mol % 3
2
SCF 3 CO CH 3
O 3 3
OH
CO, CH 3
i-Pr NH 75%
2
3 2
CH(CH ) CH(CH )
3 2
8 h
CH Pd(OAc) 2 , CH 3
3
CH CO CH PPh , Et N CH 3 CO CH
3
3
3 2 3
2 3
CH OH CH
3 CO, CH 3 3 CO CH
O SCF 2 3
3
3
93%
9 i CO CH
O SCF 3 2 3
3
H H H H
H H Pd(OAc) 2 , 5 mol % CH
O CH 3 O 3
PPh , Et N
3
3
CH O CH 3
O 3 83%
H O H OH H H O H
H CO, CH 3
Pd(PPh ) Cl ,
j 3 2 2
10
[(CH ) Si] NH
3 3
2
CH O I CH 3 O CONH 2
3
CO, DMF, 80°C
(Continued)