Page 963 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 10.13. Intramolecular Carbene-Insertion Reactions 939

1 a CH 3 CH 3 CH 3 CH 3 SECTION 10.2
1.5 equv Reactions Involving
MeO – Carbenes and Related
Intermediates
diglyme 97%
CH 3 NNHSO Ar 140°C CH 3
2
2 b CH 3
N MeO – CH 3
N
165°C
diglyme
80%
NNHSO Ar
2
3 c
O
Cu(II) CH 3
CH 3 53%
CCHN 2 THF CH 3
H C O 65°C
3
4 d O
O CH
CH 3 Rh (OAc) 4 3 H
2
N 2 25°C CH 3 CO CH 3
2
CH 3
CCCO 2 CH 3 H O
O 91%
O
5 e O
O Rh (NHCOCH ) CH 3 C
3 4
2
O
CH CCCO (CH ) CH 3
3
2
2 7
CH (CH )
2 5
3
N 2 85%
6 f
H C N hv H 2 C
2
48%
N
7 g Br Br CH 3
CH 3
CH Li
3
CH 3 –10°C
CH 3 27%
Cl
8 h 0.5 mol %
CH CH O CCHN 2
2
2
2
Rh cat
Cl
81% yield O O
95% e.e.
catalyst is tetrakis-[N-phenylpropanoyl-
4-methoxycarbonylimidazolonato] dirhodium
(Continued)