Novel Isomerically Pure Tetrasubstituted Allylboronates: Stereocontrolled Synthesis of α-Exomethylene γ-Lactones as Aldol-Like Adducts with a Stereogenic Quaternary Carbon Center

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Abstract
In spite of their inherent isomerization tendency and low reactivity, 1-alkoxycarbonyl vinylcopper(I) intermediates from the conjugate addition of organocuprates onto acetylenic esters were trapped with very high cis-addition selectivity with iodomethylboronic esters in the presence of HMPA. The resulting isomerically pure 3,3-disubstituted allylboronates react with aldehydes in a highly diastereo- and enantioselective manner, providing α-exomethylene γ-lactones with a stereogenic quaternary β-carbon center.