Development of Novel Carbon-Carbon Bond Forming Reactions by Allylic gem-Palladium/Metalloid Intermediates

In this research, we demonstrated the distinct reactivities of allylic gem-palladium/metalloid intermediates. For example, palladium-catalyzed three-component reaction of 3-(n-tributylstannyl)allyl acetates, aldehydes, and organoboranes afforded the (E)-anti-homoallylic alcohols with excellent diastereoselectivity and good to high levels of alkene stereocontrol. Moreover, we developed complementary reaction conditions to provide both (Z)- and (E)-homoallylic alcohols possessing aryl groups at the alkene terminus using a catalyst controlled strategy. The reaction showed good scope and functional group tolerance, many of which could pose difficulties for other transition-metal-catalyzed alkene isomerizations of alkenyl boronates. Thus, the catalytically generated allylic gem-palladium/boryl species promise to serve as synthetically useful intermediates.