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Beyond Hydrofunctionalisation: A Well‐Defined Calcium Compound Catalysed Mild and Efficient Carbonyl Cyanosilylation
Author(s) -
Yadav Sandeep,
Dixit Ruchi,
Vanka Kumar,
Sen Sakya S.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705795
Subject(s) - chemistry , moiety , adduct , metathesis , catalysis , iodide , combinatorial chemistry , organic chemistry , medicinal chemistry , polymerization , polymer
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(N i Pr) 2 CaI] ( 1 ) for cyanosilylation of a variety of aldehydes and ketones with Me 3 SiCN under ambient conditions without the need of any co‐catalyst. The reaction mechanism involves a weak adduct formation between 1 and Me 3 SiCN leading to the activation of the Si−C bond, which subsequently undergoes σ‐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.