Cobalt-catalyzed cross-electrophile coupling of alkynyl sulfides with unactivated chlorosilanes

Herein, we disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of a broad range of unactivated chlorosilanes with alkynyl sulfides as a stable and practical alkynyl electrophiles. Strategically, employing easily synthesized alkynyl sulfides as alkynyl precursors allows acces...

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Bibliographic Details
Published in:Nature communications 2024-05, Vol.15 (1), p.4502-4502, Article 4502
Main Authors: Xing, Donghui, Liu, Jinlin, Cai, Dingxin, Huang, Bin, Jiang, Huanfeng, Huang, Liangbin
Format: Article
Language:English
Subjects:
140/131
639/638/403/933
639/638/403/934
639/638/77/888
Base metal
Catalysts
Chlorosilanes
Cobalt
Cobalt compounds
Functional groups
High temperature
Humanities and Social Sciences
multidisciplinary
Natural products
Noble metals
Organosilicon compounds
Science
Science (multidisciplinary)
Substrates
Sulfides
Transition metals
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Summary:Herein, we disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of a broad range of unactivated chlorosilanes with alkynyl sulfides as a stable and practical alkynyl electrophiles. Strategically, employing easily synthesized alkynyl sulfides as alkynyl precursors allows access to various alkynylsilanes in good to excellent yields. Notably, this method avoids the utilization of strong bases, noble metal catalysts, high temperature and forcing reaction conditions, thus presenting apparent advantages, such as broad substrate scope (72 examples, up to 97% yield), high Csp-S chemo-selectivity and excellent functional group compatibility (Ar-X, X = Cl, Br, I, OTf, OTs). Moreover, the utilities of this method are also illustrated by downstream transformations and late-stage modification of structurally complex natural products and pharmaceuticals. Mechanistic studies elucidated that the cobalt catalyst initially reacted with alkynyl sulfides, and the activation of chlorosilanes occurred via an S N 2 process instead of a radical pathway. Transition-metal catalyzed cross-electrophile coupling (XEC) is a powerful tool for the construction of molecules but XEC between carbon electrophile and chlorosilanes to access organosilicon compounds remains underdeveloped. Here the authors disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of a broad range of unactivated chlorosilanes with alkynyl sulfides as a stable and practical alkynyl electrophiles.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-024-48873-2