Beyond hydrofunctionalisation: a well-defined calcium compound catalysed mild and efficient carbonyl cyanosilylation

TitleBeyond hydrofunctionalisation: a well-defined calcium compound catalysed mild and efficient carbonyl cyanosilylation
Publication TypeJournal Article
Year of Publication2018
AuthorsYadav, S, Dixit, R, Vanka, K, Sen, SS
JournalChemistry-A European Journal
Volume24
Issue6
Pagination1269-1273
Date PublishedJAN
Type of ArticleArticle
ISSN0947-6539
KeywordsCa catalysis, carbonyls, cyanosilylation, Density functional calculations, transition-metal free
Abstract

Organocalcium compounds have been reported as efficient catalysts for various transformations, for cases in which one of the substrates contained an E-H (E=B, N, Si, P) bond. Here, we look at the possibility of employing an organocalcium compound for a transformation in which none of the precursors has a polar E-H bond. This study demonstrates the utilization of a well-defined amidinatocalcium iodide, [PhC(NiPr)(2)CaI] (1) for cyanosilylation of a variety of aldehydes and ketones with Me3SiCN under ambient conditions without the need of any co-catalyst. The reaction mechanism involves a weak adduct formation between 1 and Me3SiCN leading to the activation of the Si-C bond, which subsequently undergoes sigma-bond metathesis with a C=O moiety. Such a mechanistic pathway is unprecedented in alkaline earth metal chemistry. Experimental and computational studies support the mechanism.

DOI10.1002/chem.201705795
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

5.317

Divison category: 
Catalysis and Inorganic Chemistry
Physical and Materials Chemistry