Issue 47, 2016

Mechanistic implications of the enantioselective addition of alkylzinc reagents to aldehydes catalyzed by nickel complexes with α-amino amide ligands

Abstract

The enantioselective alkylation of aldehydes catalysed by nickel(II)-complexes derived from α-amino amides was studied by means of density functional theory (DFT) and ONIOM (B3LYP:UFF) calculations. A mechanism was proposed in order to investigate the origin of enantioselectivity. The chirality-determining step for the alkylation was the formation of the intermediate complexes with the involvement of a 5/4/4-fused tricyclic transition state. The predominant products predicted theoretically were of (S)-configuration, in good agreement with experimental observations. The scope of the reaction was examined and high yields and enantioselectivities were observed for the enantioselective addition of Et2Zn and Me2Zn to aromatic and aliphatic aldehydes.

Graphical abstract: Mechanistic implications of the enantioselective addition of alkylzinc reagents to aldehydes catalyzed by nickel complexes with α-amino amide ligands

Supplementary files

Article information

Article type
Paper
Submitted
26 Aug 2016
Accepted
04 Nov 2016
First published
04 Nov 2016

Org. Biomol. Chem., 2016,14, 11125-11136

Mechanistic implications of the enantioselective addition of alkylzinc reagents to aldehydes catalyzed by nickel complexes with α-amino amide ligands

J. Escorihuela, M. I. Burguete, G. Ujaque, A. Lledós and S. V. Luis, Org. Biomol. Chem., 2016, 14, 11125 DOI: 10.1039/C6OB01878E

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