Anaerobic photoinduced Cu(0/I)-mediated Glaser coupling in a radical pathway

Siqi Zhang and Liang Zhao ()
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Siqi Zhang: Tsinghua University
Liang Zhao: Tsinghua University

Nature Communications, 2023, vol. 14, issue 1, 1-8

Abstract: Abstract The reaction mechanism of the historic copper-catalyzed Glaser coupling has been debated to be based on redox cycles of Cu ions in specific oxidation states or on a radical mechanism based on Cu(0)/Cu(I). Here, the authors demonstrate two coexisting Glaser coupling pathways which can be differentiated by anaerobic/irradiation or aerobic reaction conditions. Without O2, copper(I) acetylides undergo a photo-excited pathway to generate highly reactive alkynyl radicals, which combine together to form a homo-coupling product or individually react with diverse X-H (X = C, N, O, S and P) substrates via hydrogen atom transfer. With O2, copper(I) acetylides are oxidized to become a Cu-acetylide/Cu-O merged Cu(I/II) intermediate for further oxidative coupling. This work not only complements the radical mechanism for Glaser coupling, but also provides a mild way to access highly energetic alkynyl radicals for efficient organic transformations.

Date: 2023
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DOI: 10.1038/s41467-023-42602-x

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