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The stereochemical outcome observed upon alkylation of enolates derived from N-1-(1'-naphthyl)ethyl-O-tert-butylhydroxamates (chiral Weinreb amide equivalents) may be rationalized by a chiral relay mechanism. Deprotonation with KHMDS leads to a nonchelated (Z)-enolate in which the oxygen atoms adopt an anti-periplanar conformation. The configuration of the N-1-(1'-naphthyl)ethyl group dictates the conformation of the O-tert-butyl group and the configuration adopted by the adjacent pyramidal nitrogen atom. Highly diastereoselective enolate alkylation then proceeds anti to both the bulky tert-butyl group (sterically driven) and the N-lone pair (stereoelectronically driven).

Original publication

DOI

10.1021/jo902499s

Type

Journal article

Journal

J Org Chem

Publication Date

19/02/2010

Volume

75

Pages

1214 - 1227

Keywords

Alkylation, Bridged Bicyclo Compounds, Crystallography, X-Ray, Hydroxamic Acids, Molecular Structure, Naphthalenes, Stereoisomerism, Ultraviolet Rays