Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2021 Apr 7;143(13):4935-4941. doi: 10.1021/jacs.1c01880. Epub 2021 Mar 24.
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.
我们报告了一种通过 CuH 催化的对烯丙基的对映选择性加氢甲酰化反应来制备 α-手性羧酸衍生物的方法，包括那些带有全碳季碳原子的衍生物。该方法可以容忍烯丙基上的各种杂环和官能团，以优异的对映选择性和区域选择性得到高收率的手性 α-季碳和叔碳羧酸衍生物。该方法的合成实用性进一步通过对产物的衍生化来证明，得到了包括抗血小板药物吲哚布芬在内的具有重要生物学意义的化合物。
