Z-Selective Semihydrogenation of Alkynes Catalyzed by a Co(I)PCNHCP Pincer Complex: A Simple, Fast, and Practical Methodology

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-03-18 DOI:10.1021/acscatal.5c00792

Tofayel Sheikh Mohammad, Pavel Sakharov, Sakthi Raje, Graham de Ruiter

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Abstract

The stereoselective synthesis of alkenes from their corresponding internal alkynes is a highly desirable and atom-economical reaction that is typically performed via transfer hydrogenation. Very few practical methods have been developed that allow for the direct hydrogenation of alkynes under mild reaction conditions and with high stereoselectivities. Here, we demonstrated that a well-defined cobalt catalyst [(PC_NHCP)Co(N₂)][BAr₄^F] (1) catalyzes the semihydrogenation of alkynes under mild conditions (25 °C; 1 bar H₂) and with high stereoselectivities (>99:1). The reaction does not require any additives, is fast (<60 min), and is compatible with a variety of functional groups that include aldehydes, ketones, esters, and alcohols. Even natural products can be used with our hydrogenation protocol highlighting its versatility. Our mechanistic studies indicate the presence of a transient Co(III)-dihydride that is responsible for the hydrogenation of the herein reported internal and terminal alkynes.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.