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A mechanistic study of oxygen atom transfer from N-sulfonyloxaziridine to enolates
- Source :
- Tetrahedron. 75:2056-2061
- Publication Year :
- 2019
- Publisher :
- Elsevier BV, 2019.
-
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.
- Subjects :
- Steric effects
010405 organic chemistry
Organic Chemistry
chemistry.chemical_element
010402 general chemistry
01 natural sciences
Biochemistry
Oxaziridine
0104 chemical sciences
Metal
chemistry.chemical_compound
Oxygen atom
chemistry
Computational chemistry
visual_art
Drug Discovery
visual_art.visual_art_medium
Reactivity (chemistry)
Chelation
Lithium
Subjects
Details
- ISSN :
- 00404020
- Volume :
- 75
- Database :
- OpenAIRE
- Journal :
- Tetrahedron
- Accession number :
- edsair.doi...........fa1260b3f86d5f750ac60229f47d1c74