Page 761 - Advanced Organic Chemistry Part B - Reactions & Synthesis

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Scheme 8.12. Palladium-Catalyzed Coupling of Stannanes with Halides and Sulfonates SECTION 8.2
Reactions Involving
A. Aryl halides Organopalladium
Intermediates
1 a
Pd(PPh )
O Br + CH CHCH Sn(n -Bu) 3 4
CH 3 2 2 3 CH O CH CH CH 2
2
3
120°C, 20 h
96%
2 b Pd(PPh )
O N Br + CH CHSn(n -Bu) 3 4 O 2 N CH CH 2
2 2 3 105°C, 4 h
80%
3 c
PdCl (PPh )
2 3 2
CH O SnBu 3 + CF SO O NO 2 CH O OCH 3
3
3 3 2
LiCl , DMF
2
48%
4 d Br
Pd(PPh ) 4 , 10 mol %
3
+ AgO, 1 equiv, N
N Sn(n -Bu) 3 DMF, 100°C 70%
N N
5 e
O OCH(CH ) O OCH(CH )
3 2
3 2
PhCH 2 Pd(PPh 3 ) 2 Cl, 5 mol %
+ I OCH 3 CuI, 10 mol %
O Sn(n -Bu) DMF O
3
80%
OCH
3
B. Alkenyl halides and sulfonates
6 f PdCl 2 (CH CN)
PhCH CHI + CH 2 CHSn(n -Bu) 3 3 2 PhCH CHCH CH 2
25°C, 0.1 h 85%
7 g H
CH 3 CH H CH 3 CH 3 Si(CH 3 ) 3
3 3
3 (CH ) Sn Pd(PPh ) C
3 4
OSO CF + C C C
2 3
)
H Si(CH 3 3 CH H 100%
3
CH 3
8 h
O Pd(CH CN) Cl O
3 2 2 CH 3
5 mol %
I (n -Bu) Sn
+ 3 CH 3
Ph As, 10 mol %
3
CH NMP, 100°C CH
3 3
9 i CH
CH 3 Pd(PPh ) 3 4 3
Sn(n -Bu) + O CH OH
O 3 I CH 2 OH THF, DMF 2
OTBDMS CH 3 OTBDMS CH 3 42%
10 j
3
HO I O CC(CH )3 Pd(CH CN) Cl , 2.5 mol %
2
3
2
2
+
O 2 CC(CH 3 ) 3
DMF
TBDMSO OTBDMS (n -Bu) Sn CH 3
3
HO
CH
82% 3
TBDMSO OTBDMS
11 k CO CH 3
2
O SCF 3 CO CH 3 Pd (dba) , 5 mol %
2
3
+ 2 3 NHCO C(CH )
Ph As, 10 mol % 2 3 3
(n -Bu) Sn NHCO C(CH ) 3
Ph 3 2 3 3 85%
DMF Ph
(Continued)