Development of highly selective allylic cyanation through an electrophilic approach

2019 Fiscal Year Final Research Report

• Project/Area Number: 18K14217
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Osaka University
• Principal Investigator: Kensuke Kiyokawa 大阪大学, 工学研究科, 助教 (80632364)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Keywords: ホウ素 / アリルボラン / ニトリル / シアノ化 / 選択的反応

Outline of Final Research Achievements

The electrophilic cyanation of allylic boranes, which were prepared in situ by hydroboration of allenes or cyclic 1,3-dienes with 9-BBN, using TsCN or NCTS as a cyanating reagent was developed to provide efficient access to β,γ-unsaturated nitriles. The cyanation proceeds with complete allylic transposition, and therefore, β,γ-unsaturated nitriles containing allylic quaternary carbon centers, which are difficult to access by existing methods, could be synthesized by employing γ,γ-disubstituted allylic boranes.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究では、従来の求核的なシアノ化反応では合成が極めて困難であったアリル位に第四級炭素を有する β,γ-不飽和ニトリルの合成を達成した。本成果は、合成化学的に有用なニトリル類の新たな合成指針を提供するとともに、有機ホウ素化合物の新たな反応性を開拓した、という点において有機合成化学分野において重要な成果であると言える。