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Computational Investigations on the General Reaction Profile and Diastereoselectivity in Sulfur Ylide Promoted Aziridination
Author(s) -
Janardanan Deepa,
Sunoj Raghavan B.
Publication year - 2007
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.200700303
Subject(s) - ylide , transition state , chemistry , steric effects , sulfur , aziridine , computational chemistry , solvent , medicinal chemistry , density functional theory , photochemistry , catalysis , organic chemistry , ring (chemistry)
Mechanism and diastereoselectivity of sulfur ylide promoted aziridination reactions were studied by density functional theory with inclusion of solvent effects through the continuum solvation model. The general reaction pathway was modeled for the addition of substituted sulfur ylides (Me 2 S + CH − R) to an aldimine (( E )‐methyl ethylidenecarbamate, MeHCNCO 2 Me). The nature of the substituents on the ylidic carbon atom substantially affects the reaction profile. The stabilized (R=COMe) and semistabilized (R=Ph) ylides follow a cisoid addition mode leading to trans aziridines via anti betaine intermediates. The simplest model ylide (unstabilized, R=H) underwent cisoid addition in a similar fashion. In the case of stabilized ylides product diastereoselectivity is controlled by the barriers of the elimination step leading to the 2,3‐ trans aziridine, whereas it is decided in the addition step in the case of semistabilized ylides. The importance of steric and electronic factors in diastereoselective addition ( 2 and 5 ) and elimination ( 5 ) transition states was established. Comparison of results obtained with the gas‐phase optimized geometries and with the fully optimized solvent‐phase geometries reveals that the inclusion of solvent effects does not bring about any dramatic changes in the reaction profiles for all three kinds of ylides. In particular, diastereoselectivity for both kinds of ylides was found to be nearly the same in both these approaches.