Rhodium catalysts with superbulky NHC ligands for the selective α-hydrothiolation of alkynes.

[en] Eight rhodium complexes-including four new compounds-with the generic formula [RhCl(cod)(NHC)] (cod is 1,3-cyclooctadiene) differing by the size of their N-heterocyclic carbene (NHC) ligand were prepared, characterized, and found to be catalytically active in the hydrothiolation of terminal alkynes with aliphatic or aromatic thiols. The steric bulk of the carbene was found to markedly influence the reaction rate and selectivity. In particular, superbulky NHCs led to the almost quantitative formation of the sole α-vinyl sulfide products. The experimental conditions were optimized to allow the straightforward synthesis of a broad range of mono- and disubstituted α-adducts starting from terminal alkynes (18 examples) and thiols (5 examples). Altogether, the procedure devised in this study provides an easy access to α-vinyl sulfides with full atom economy and a low catalyst loading.

Disciplines :

Chemistry

Author, co-author :

Bołt, Małgorzata ; Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89B, 61-614 Poznan, Poland. pkw@amu.edu.pl

Delaude, Lionel ; Université de Liège - ULiège > Molecular Systems (MolSys)

Żak, Patrycja ; Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89B, 61-614 Poznan, Poland. pkw@amu.edu.pl

Language :

English

Title :

Rhodium catalysts with superbulky NHC ligands for the selective α-hydrothiolation of alkynes.

Publication date :

15 March 2022

Journal title :

Dalton Transactions

ISSN :

1477-9226

eISSN :

1477-9234

Publisher :

Royal Society of Chemistry, England

Volume :

Issue :

Pages :

4429-4434

Peer reviewed :

Peer reviewed

Additional URL :

http://pubs.rsc.org/en/content/articlepdf/2022/DT/D2DT00243D

Funders :

Narodowe Centrum Nauki

Funding text :

The authors gratefully acknowledge the financial support from the National Science Centre (Poland) (SONATA Project No. UMO-2016/23/D/ST5/00417).

Available on ORBi :

since 12 April 2022

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