Iron-catalysed highly selective hydroalkoxycarbonylation of alkynes using CO as C1 source

TitleIron-catalysed highly selective hydroalkoxycarbonylation of alkynes using CO as C1 source
Publication TypeJournal Article
Year of Publication2023
AuthorsTewari, T, Kumar, R, Chikkali, SH
JournalCatalysis Science & Technology
Volume13
Issue19
Pagination5549-5555
Date PublishedOCT
Type of ArticleArticle
ISSN2044-4753
Abstract

Though precious and rare, late-transition metals have been extensively used in metal-catalysed carbonylation reactions in organic transformations. On the other hand, base metals are abundant and cheap, but their practical utilization in carbonylation reactions is rarely explored. Here, we report iron-catalysed hydroalkoxycarbonylation of alkynes to alpha,beta-unsaturated esters in one pot. A readily available iron precursor [Fe2(CO)9] in the presence of a diimine ligand L7 catalyzes the conversion of alkynes to alpha,beta-unsaturated esters under 10 bar CO pressure. This operationally simple protocol tolerates various functional groups and allows facile access to about 40 alpha,beta-unsaturated esters. The synthetic utility of the reaction has been demonstrated by scaling up the reaction to 1 g and by preparing sunscreen/antifungal agents. The kinetic study suggests that the reaction is an approximate 1st order with respect to the iron catalyst, and the initial rate of the reaction is 3.6 x 10-2 M h-1. Mechanistic investigations using NMR spectroscopy indicated the existence of an [Fe-H] intermediate, and control experiments using a radical trapping reagent and EPR revealed the absence of any radical species in the reaction. Precious and rare, late transition metals have been extensively used in carbonylation. An earth abundant iron-catalyst is reported here for hydroalkoxycarbonylation of alkynes in the presence of CO as C1 source.

DOI10.1039/d3cy00843f
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

5.0

Divison category: 
Polymer Science & Engineering
Database: 
Web of Science (WoS)

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