Page 585 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 6.13. (Continued) 559

j H SECTION 6.4
10 O
[3,3]-Sigmatropic
NaH Rearrangements
OH CH 3 THF CH 2
CH 2
CH 2 CH 88%
3
O
11 k
CH 3 O H C O
3
CH 3 CH 3
OCH 3 NaH
OH O
O THF O
CH 3 CH 3 H O OCH 3 97%
C. Siloxy-Cope
12 l OCH OPMP
2
O OTES
TESO
CH 2 135°C
OTBDPS O OCH OPMP
2
13 m O O TBDPSO 99%
R SiO O CH Ph R SiO CH 3 O CH 2 Ph
2
3
180°C 3
N N O
3 h
O CH 3
O O
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The reaction in Entry 5 is a case in which the thermal conditions were preferable to the
basic conditions because of the base sensitivity of the product. Entries 6 to 10 show
anionic oxy-Cope reactions. Entries 6 and 7 are early examples of the application of
the reaction in synthesis. Entries 8 and 9 involve rearrangements of bicyclo[2.2.1]hept-
2-en-2-ol derivatives to give cis-fused bicyclo[4.3.0]non-7-en-3-ones.

H H
R R
O – O –
O – R O
R
The rearrangement in Entry 9 occurs spontaneously on warming of the reaction mixture
from addition of an organolithium reagent to form the vinyl carbinol unit. This is a
very general means of constructing reactants for oxy-Cope rearrangements that leads