Synthetic Chemistry of Allenic Compounds Catalyzed/Mediated by Transition-Metal Species

2014 Fiscal Year Final Research Report

• Project/Area Number: 24350044
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: OGASAWARA Masamichi 北海道大学, 触媒化学研究センター, 准教授 (70301231)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: アレン / 遷移金属触媒 / 軸不斉 / 天然物 / 不斉合成 / 均一系触媒

Outline of Final Research Achievements

Synthetic chemistry of allenic compounds, which are important synthones in organic chemistry, has been developed using various transition-metal speceis. It was found that the use of BDT, which is a cyclic bissulfone, as a pronucleophile in the palladium-catalyzed allene synthesis reaction afforded the corresponding axially chiral allenes in high yields with excellent enantioselectivity. This novel reaction conditions enabled us to access various alkyl-substituted allenes, and thus the asymmetric total synthesis of a wide range of naturally occurring allenes could be realized.
Easily accessible 3-bromopenta-2,4-dienyl acetate was applied to the palladium-catalyzed reaction with soft nucleophiles. The reaction proceeded through the stepwise twofold nucleophilic substitution via formal SN2'- and SN2-processes giving the various doubly functionalized C2-symmetric allenes in good yields.

Free Research Field

有機金属化学