脱羧烷基化炔烃反应。
Decarboxylative Hydroalkylation of Alkynes.
机构信息
Merck Center for Catalysis at Princeton University , Princeton , New Jersey 08544 , United States.
出版信息
J Am Chem Soc. 2018 May 2;140(17):5701-5705. doi: 10.1021/jacs.8b02834. Epub 2018 Apr 20.
Abstract
The merger of open- and closed-shell elementary organometallic steps has enabled the selective intermolecular addition of nucleophilic radicals to unactivated alkynes. A range of carboxylic acids can be subjected to a CO extrusion, nickel capture, migratory insertion sequence with terminal and internal alkynes to generate stereodefined functionalized olefins. This platform has been further extended, via hydrogen atom transfer, to the direct vinylation of unactivated C-H bonds. Preliminary studies indicate that a Ni-alkyl migratory insertion is operative.
摘要
开壳和闭壳元素有机步骤的合并使得亲核自由基能够选择性地与未活化的炔烃进行分子间加成。一系列羧酸可以进行 CO 挤出、镍捕获、与末端和内部炔烃的迁移插入序列反应，生成立体定义的官能化烯烃。该平台通过氢原子转移进一步扩展到未活化的 C-H 键的直接乙烯基化。初步研究表明，Ni-烷基迁移插入是可行的。
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