美国麻省理工学院Stephen L. Buchwald等近日发展了CuH催化的联烯区域和对映选择性加氢羧酸化反应，以合成具有开环季碳中心的羧酸。这一研究成果于2021年3月24日发表在国际顶尖学术期刊《美国化学会杂志》上。

课题组人员报告了一种方法，可通过CuH催化的联烯与商品化的氟甲酸酯的对映选择性加氢羧化反应，来制备α-手性羧酸衍生物，包括含全碳取代的季碳中心的羧酸。该方法可兼容联烯上各种杂环和取代基，并以较好的产率生成手性富集的α-季碳或叔碳羧酸衍生物，且区域选择性上只产生分叉的产物。

在进一步研究中，该方法的合成用途通过进一步衍生产物以合成具有重要生物活性的化合物，例如抗血小板药物吲哚布芬，得到了验证。

附：英文原文

Title: CuH-Catalyzed Regio- and Enantioselective Hydrocarboxylation of Allenes: Toward Carboxylic Acids with Acyclic Quaternary Centers

Author: Sheng Feng, Stephen L. Buchwald

Issue&Volume: March 24, 2021

Abstract: We report a method to prepare α-chiral carboxylic acid derivatives, including those bearing all-carbon quaternary centers, through an enantioselective CuH-catalyzed hydrocarboxylation of allenes with a commercially available fluoroformate. A broad range of heterocycles and functional groups on the allenes were tolerated in this protocol, giving enantioenriched α-quaternary and tertiary carboxylic acid derivatives in good yields with exclusive branched regioselectivity. The synthetic utility of this approach was further demonstrated by derivatization of the products to afford biologically important compounds, including the antiplatelet drug indobufen.

DOI: 10.1021/jacs.1c01880

Source: https://pubs.acs.org/doi/10.1021/jacs.1c01880