Mechanistic insights into rare-earth-catalysed C-H alkylation of sulfides: sulfide facilitating alkene insertion and beyond

RSC Adv. 2022 May 5;12(22):13593-13599. doi: 10.1039/d2ra02180c. eCollection 2022 May 5.

ABSTRACT

The catalytic C-H alkylation with alkenes is of much interest and importance, as it offers a 100% atom efficient route for C-C bond construction. In the past decade, great progress in rare-earth catalysed C-H alkylation of various heteroatom-containing substrates with alkenes has been made. However, whether or how a heteroatom-containing substrate would influence the coordination or insertion of an alkene at the catalyst metal center remained elusive. In this work, the mechanism of Sc-catalysed C-H alkylation of sulfides with alkenes and dienes has been carefully examined by DFT calculations, which revealed that the alkene insertion could proceed via a sulfide-facilitated mechanism. It has been found that a similar mechanism may also work for the C-H alkylation of other heteroatom-containing substrates such as pyridine and anisole. Moreover, the substrate-facilitated alkene insertion mechanism and a substrate-free one could be switched by fine-tuning the sterics of catalysts and substrates. This work provides new insights into the role of heteroatom-containing substrates in alkene-insertion-involved reactions, and may help guide designing new catalysis systems.

PMID:35530397 | PMC:PMC9069833 | DOI:10.1039/d2ra02180c

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