Development of Catalytic Carboxylation of C(sp3)-H Bonds with Carbon Dioxide

2016 Fiscal Year Final Research Report

• Project/Area Number: 26410108
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: MITA Tsuyoshi 北海道大学, 薬学研究院, 助教 (00548183)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Keywords: 二酸化炭素 / C-H結合活性化 / カルボキシル化 / C(sp3)-H結合 / 遷移金属錯体 / コバルト / トリメチルアルミニウム / ラクトン

Outline of Final Research Achievements

A catalytic carboxylation of the allylic C(sp3)-H bond of terminal alkenes with CO2 was developed with the aid of a cobalt/Xantphos complex. A wide range of allylarenes and 1,4-dienes were successfully transformed into the linear styrylacetic acid and hexa-3,5-dienoic acid derivatives in moderate to high yields, with excellent regioselectivity. The carboxylation showed remarkable functional group tolerability, so that selective addition to CO2 occurred in the presence of other carbonyl groups such as amide, ester, and ketone. Since styrylacetic acid derivatives can be readily converted into optically active γ-butyrolactones through Sharpless asymmetric dihydroxylation, this allylic C(sp3)-H carboxylation showcases a facile synthesis of γ-butyrolactones from simple allylarenes via short steps.

Free Research Field

有機合成化学