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A reviewer raised the point that if the cis-γ-hydroxy enones exist as the alkoxides under the basic reaction conditions then attack by the phosphonate nucleophile may occur from the opposite face to that described in Scheme 1, giving rise to intermediate A. Collapse of this intermediate via a SNi (frontside) displacement would then give rise to the cyclopropane diastereoisomer B in the opposite enantiomeric series, Chemical Equation Presented) The following scheme outlines the synthesis of cyclopropane D from trans-γ-hydroxy enone C (reaction of which proceeds via the cis γ-hydroxyenone)36 of known absolute stereochemistry. The absolute stereochemistry of cyclopropane D was established by single-crystal X-ray crystallography and supports the mechanism for cyclopropanation shown in Scheme 1 and rules out the alternative depicted above.52 Chemical Equation Presented
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