A mechanistic study of oxygen atom transfer from N-sulfonyloxaziridine to enolates |
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Authors: | Hayden C Foy Adrian L Schwan Travis Dudding |
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Institution: | 1. Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catherines, ON, L2S 3A1, Canada;2. Department of Chemistry, University of Guelph, 50 Stone Rd E, Guelph, ON, N1G 2W1, Canada |
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Abstract: | Enolate additions to chiral N-sulfonyloxaziridines providing enantiomerically enriched α-hydroxy carbonyl compounds is a reaction of importance, yet a clear understanding of the factors governing stereoinduction in these transformations remains ambiguous. This is despite, previous computational studies, one by Bach et al. employing truncated model systems exploring oxygen atom transfer to an unsubstituted lithium enolate and another by our own group. In clarifying this reactivity we report here a computational study examining oxygen atom transfer from 1-S-(+)-(10-camphorsulfonyl)oxaziridine, viz., archetypal Davis chiral oxaziridine to substituted Li, Na, K enolates offering improved mechanistic understanding. From this investigation, a revised model is offered revealing the metal cation, chelation effects and sterics as decisive stereocontrolling factors in enolate additions to chiral N-sulfonyloxaziridines affording enantiomerically enriched α-hydroxy carbonyl compounds. |
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Keywords: | Density functional theory Chiral oxaziridines Asymmetric α-hydroxylation Non-covalent interactions Enantiomerically enriched α-hydroxy carbonyl compounds |
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