Abstract
Ethenylcyclopropane (5 ) was prepared
from cyclopropyl methyl ketone (1 ) in four
simple, easily scalable steps (bromination, reduction to the bromohydrin,
acetylation of the latter, and reductive elimination with Zn/Cu)
in an overall yield of 56%. 1-Bromo-2-cyclopropylcyclopropane
(7 ) (approximately 1:1 mixture of cis - and trans -7 ) was
prepared from 5 via the dibromide 6 , and from 7 the
boronate cis /trans -8 (ratio 1:1) was obtained in 96% yield.
Rhodium(II)-catalyzed cyclopropanation of 5 with
ethyl diazoacetate gave ethyl 2-cyclopropylcyclopropanecarboxylate
(cis /trans -9 , ratio 1:1.4) in 80% yield.
The latter was also prepared in 79% overall yield by sequential
cyclopropanation of buta-1,3-diene with ethyl diazoacetate [under
Rh2 (OAc)4 catalysis] and diiodomethane/diethylzinc/trifluoroacetic
acid. Curtius degradation of 2-cyclopropylcyclopropanecarboxylic
acid (obtained by hydrolysis of the ester) gave 2-cyclopropylcyclopropanamine
(1:1.2 mixture of cis - and trans -isomers) in 58% yield.
Key words
bromination - reduction - elimination - alkenes - cyclopropanation - small rings
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