title: Stereocontrol in proline-catalyzed asymmetric amination: a comparative assessment of the role of enamine carboxylic acid and enamine carboxylate.
abstract: The transition state models in two mechanistically distinct pathways, involving (i) an enamine carboxylic acid (path-A, 4) and (ii) an enamine carboxylate (path-B, 8), in the proline-catalyzed asymmetric α-amination have been examined using DFT methods. The path-A predicts the correct product stereochemistry under base-free conditions while path-B accounts for reversal of configuration in the presence of a base.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
authors.forename: Akhilesh K
authors.initials: AK
authors.lastname: Sharma
authors.forename: Raghavan B
authors.initials: RB
authors.lastname: Sunoj
mesh_terms: D000586:Amination; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D011392:Proline / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D002264:Carboxylic Acids; D011392:Proline