Development of novel reactions using carbonyls as latent nucleophiles

2020 Fiscal Year Final Research Report

• Project/Area Number: 18H01971
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Kanazawa University
• Principal Investigator: Ohmiya Hirohisa 金沢大学, 薬学系, 教授 (40508876)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Keywords: ラジカル反応 / カルベン触媒 / 銅触媒 / 有機触媒 / 不斉触媒

Outline of Final Research Achievements

The researcher found a radical NHC catalysis enabling decarboxylative cross-coupling reactions of tertiary/secondary, redox-active esters derived from alkyl carboxylic acids with aldehydes to generate ketones. Additionally, the radical NHC catalysis could be employed with the alkylacylation of acrylonitriles, acylates and styrenes with redox esters obtained from tertiary alkyl carboxylic acids and aldehydes, via a radical relay mechanism.
The researcher achieved reductive umpolung using a copper catalyst and a silylboronate to convert an aldehyde to a nucleophilic α-silyloxyalkylcopper(I) species. The α-silyloxyalkylcopper(I) species, generated via addition of the silylcopper(I) species to an aldehyde followed by [1,2]-Brook rearrangement, could react with various electrophiles to afford a series of alcohol derivatives.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究によって見出された分子変換反応により、多様な有機分子へのアプローチにおいて柔軟性が格段に増すと考えられる。そして、従来の変換手法に比べて圧倒的な省資源、低エネルギー、低環境負荷、低コスト化を可能とする理想的な変換プロセスに繋げることができる。