Herein, we report a straightforward approach to access 1,4-dicarboxylic acid diesters via BiPyPhos-enabled cobalt-catalyzed bis-alkoxycarbonylation of alkynes. This strategy utilizes an earth-abundant and cost-efficient cobalt catalyst, free from acid additives or noble metal catalysts. The bifunctional ligand BiPyPhos plays a crucial character in both the rate-determining step and the stability of the cobalt catalytic system. The reaction delivers the product directly with an associative abstraction process. Mechanism studies coupled with NMR, FI-IR, HRMS, and single-crystal X-ray analysis indicate that the carbonyl cobalt hydride complex might be the catalytically active species. Utilizing CoCl for bis-alkoxycarbonylation of alkynes has hardly any precedent.

中文翻译：

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双功能二膦配体钴催化炔烃双烷氧基羰基化

在此，我们报告了一种通过 BiPyPhos 钴催化的炔烃双烷氧基羰基化获得 1,4-二羧酸二酯的简单方法。该策略使用地球上储量丰富且经济高效的钴催化剂，不含酸添加剂或贵金属催化剂。双功能配体 BiPyPhos 在钴催化体系的限速步骤和稳定性中起着至关重要的作用。该反应通过关联抽象过程直接产生产物。机理研究结合 NMR、FI-IR、HRMS 和单晶 X 射线分析表明，羰基氢化钴络合物可能是催化活性物质。利用 CoCl 进行炔烃的双烷氧基羰基化几乎没有任何先例。