Topics in Current Chemistry, 1988, Volume 144/1988, 1-71, DOI: 10.1007/BFb0111228

Synthesis and synthetic applications of 1-donor substituted cyclopropanes with ethynyl, vinyl and carbonyl groups

Jacques R. Y. Salaün

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Abstract

Substituted on the same carbon by an electron donating group and an adjacent multiple bond, cyclopropanes provide building blocks of unprecedented synthetic potential. They are readily available along different routes involving: cyclopropanone hemiacetals, oxaspiropentanes, alkylidenecyclopropanes, 1-heterosubstituted lithiocyclopropanes, α-enone silyl enol ethers, 1,3-dichloroacetone and 1-hydroxycyclopropylcarbonyl derivatives as main sources.
First of all, they undergo acid-induced C3→C4 ring expansion to four-membered rings, in particular to the 2-vinylcyclobutanone system, which is an efficient precursor of C5, C6 and C8 homologous rings by subsequent acid- and base-induced, thermal, or photolytic ring enlargements. On the other hand, they undergo thermal C3→C5 ring expansion providing cyclopentanone enol ethers or derivatives with high chemo-, regio- and stereoselectivity.

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