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

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 alpha-exomethylene gamma-lactones with a stereogenic quaternary beta-carbon center.