Cobalt-catalyzed synthesis of amides from alkenes and amines promoted by light

• 成果类型: Article
• 署名作者: Faculak, Mason S.; Veatch, Alexander M.; Alexanian, Erik J.
• 署名单位: University of North Carolina; University of North Carolina Chapel Hill
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-13269
• DOI: 10.1126/science.adk2312
• 发表日期: 2024-01-05
• 页码: 77-81
• 关键词: olefins; hydroaminocarbonylation; aminocarbonylation; hydroformylation; generation

摘要

Catalytic methods to couple alkene and amine feedstocks are valuable in synthetic chemistry. The direct carbonylative coupling of alkenes and amines holds promise as a perfectly atom-economical approach to amide synthesis, but general methods remain underdeveloped. Herein, we report an alkene hydroaminocarbonylation catalyzed by unmodified, inexpensive cobalt carbonyl under mild conditions and low pressure promoted by light. Silane addition after the reaction enables sequential cobalt-catalyzed amide reduction, constituting a formal alkene hydroaminomethylation. These methods exhibit exceptional scope across both alkene and amine components with high chemo- and regioselectivity and proceed efficiently even in the absence of solvent. The formation of a hydridocobalt through photodissociation of a carbonyl ligand is proposed to enable catalytic activity under mild conditions, which addresses a long-standing challenge in catalysis.