Diastereoselective Syntheses of Highly Substituted Methylenecyclopropanes via Copper- or Iron-Catalyzed Reactions of 1,2-Disubstituted 3-(Hydroxy­methyl)cyclopropenes with Grignard Reagents

Dedicated to Scott Denmark in recognition of his contributions to the chemistry of strained molecules

Abstract

Described are diastereoselective syntheses of highly substituted methylenecyclopropanes from 1,2-disubstituted 3-(hydroxymethyl)cyclopropenes with allylic ether leaving groups, compounds that were constructed via alkylation of cyclopropenecarboxylic acid dianions. Substitution reactions of 1,2-disubstituted 3-(hydroxymethyl)cyclopropenes with Grignard reagents proceed with good yield and high diastereoselectivity. Under copper(I)-catalyzed conditions, the substitution reactions proceed to give syn-addition products, whereas Fe(acac)₃ catalysis gives the products of anti-addition.

Key words

cyclopropene - diastereoselective - dianion - methylenecyclopropane - substitution

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