Page 1022 - Advanced Organic Chemistry Part B - Reactions & Synthesis

998 O
(h) Ph Ph
OCH 3
TMSO
CHAPTER 10 C CH 2
(CH 3 ) 3 SiO 3 SCF 3
(CH 2 ) 2 CH(OCH 3 ) 2
Reactions Involving 2,6-di-t-butylpyridine H
Carbocations, Carbenes,
and Radicals as Reactive 90% yield, 2:1 mixture of stereoisomers
Intermediates
(i)
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3 N Bu 3 SnH CH 2 CH 3
OC N
O AIBN O + O
CH 3 CH 3
S
CH(CH 3 ) 2 CH 3
53% 14%
O
(j)
O Ph cat PhSH
+
CH CH 2 CHCO 2 C(CH 3 ) 3
O Ph CH 2
CH 2 CH
CO 2 C(CH 3 ) 3
51%
(k) Br
Bu 3 SnH
CO 2 C 2 H 5 CH 2 CO 2 C 2 H 5
(C 2 H 5 ) 3 B
O O H 67%
(l) PhCH 2 N 2 O
O CO 2 C 2 H 5
N Rh 2 (O 2 CC 4 F 9 ) 4
N
CO 2 C 2 H 5
CH 3 O O
PhCH 2
CH 3
(m)
CH 3 CO 2 O PhCONH CH 3 CO 2 O
PhCONH OH O
O CH 3 CH 3 CH 3 CH 3 CH O
OTs
+ –
n-Bu 4 N F Ph
Ph O O
THF CH 2 O 2 CCH 3
OTBDMS O OTBDMS HO H
HO OH
PhCO 2
O 2 CCH 3 PhCO 2
(n) CH CO 2 CH 3
CH 2 CH CH 2 CH
O
CH 2
Cu(acac) 2
O O N 2 O
CH
CH 2 O
CO 2 CH 3 64%
CH 3
O CH 3
(o)
CO 2 C 2 H 5
CH 2 CO 2 C 2 H 5
O N Bu 3 SnH O N O N
AIBN +
CO 2 C 2 H 5
Br 64% 6%
(p)
CH 3
CH 3
CH 3
CH 2 CH O
O O CH 3
0.4 eq BF 3
CH 3
Ph –15°C Ph 90%
CH 3
CH 3
CH 3