Unprecedented Mo3S4 cluster-catalyzed radical C-C cross-coupling reactions of aryl alkynes and acrylates

Juanjo Mateu-Campos, Eva Guillamón, Vicent S. Safont, Kathrin Junge, Henrik Junge, Matthias Beller, Rosa Llusar

Research output: Contribution to journalArticlepeer-review

Abstract

A new method for the generation of benzyl radicals from terminal aromatic alkynes has been developed, which allows the direct cross coupling with acrylate derivatives. Our additive-free protocol employs air-stable diamino Mo3S4 cubane-type cluster catalysts in the presence of hydrogen. A sulfur-centered cluster catalysis mechanism for benzyl radical formation is proposed based on catalytic and stoichiometric experiments. The process starts with the cluster hydrogen activation to form a bis(hydrosulfido) [Mo33-S)(μ-S)(μ-SH)2Cl3(dmen)3]+ intermediate. The reaction of various aromatic terminal alkynes containing different functionalities with a series of acrylates affords the corresponding Giese-type radical addition products.

Original languageEnglish
Pages (from-to)4147-4153
Number of pages7
JournalDalton Transactions
Volume53
Issue number9
DOIs
StatePublished - 30 Jan 2024
Externally publishedYes

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