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

2017 Fiscal Year Final Research Report

• Project/Area Number: 15K05496
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: University of Toyama
• Principal Investigator: Horino Yoshikazu 富山大学, 大学院理工学研究部(工学), 准教授 (30447651)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Keywords: パラジウム / ホモアリルアルコール / アリル化反応 / 不斉転写 / アリルパラジウム / 三成分連結反応

Outline of Final Research Achievements

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.

Free Research Field

有機合成化学