Superiority of Phosphate Ester as Leaving Group for Organocopper Reactions. Highly SN2′ -, (E)-, and Antiselective Alkylation of Allylic Alcohol Derivatives

Abstract
Treatment of secondary allylic chlorides or allylic phosphates in tetrahydrofuran with prenyl Grignard reagent (3-methyl-2-butenylmagnesium chloride) in the presence of CuCN.2LiCl gave geraniol or farnesol derivatives with high SN2′ selectivity. Phosphate leaving groups were highly trans-stereoselective for the formation of (E, E)-farnesol derivatives. Furthermore, complete anti-SN2′ selectivity was observed in the alkylation of optically active allylic phosphates. The present method appears to be an excellent carbon-carbon coupling reaction with regio-, (E)-, and enantioselectivity.

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