Development of new catalytic C-C bond-forming reactions other than allylation reactions via alpha-silyl-substituted sigma-allylpalladium intermediates

2014 Fiscal Year Final Research Report

• Project/Area Number: 24550115
• 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): 2012-04-01 – 2015-03-31
• Keywords: パラジウム / メタロイド / アリル化 / シクロプロパン化 / 二量化 / 三成分連結反応

Outline of Final Research Achievements

We have developed new methods for the generation of putative palladacyclobutene intermediates and palladium carbenoid intermediates from　α-metalloid-substituted σ-allylpalladium intermediates. These intermediates then undergo stereoselective cyclopropanation of strained alkenes and self-dimerization of palladium carbenoid intermediates, respectively. Furthermore, the three-component reaction proceeded to provide (Z)-anti-homoallylic alcohols with high diastereoselectivities and high level of alkene stereocontrols if the metalloid-substituted allylacetates, aldehydes, and organoboranes are treated in the presence of palladium catalyst. The present reaction is believed to proceed via an allylation of aldehydes followed by coupling reaction of vinylpalladium intermediates with organoboranes. Thus, we have demonstrated that α-metalloid-substituted π-allylpalladium intermediates can be used for carbon-carbon bond forming-reaction other than allylation reactions.

Free Research Field

有機合成化学