立体発散的スキップジエン合成法の開発とマダンガミン類の網羅的全合成

抄録

A skipped diene (1,4-diene) is an important structural motif found in a variety of biologically active natural products. We report the stereodivergent method, consisting of hydroboration of allenes and the Migita-Kosugi-Stille coupling, which allows for access to all four possible stereoisomers of the skipped dienes. The hydroboration of allenes is especially useful because both E-allylic and Z-allylic alcohols are obtained by simply changing the organoborane reagent. While use of 9-BBN provides E-allylic alcohols as thermodynamic products, the reaction with HB(Sia)₂ gives Z-allylic alcohols as kinetic products. The developed method was successfully applied to the unified total synthesis of madangamine alkaloids.