title: Mechanism and selectivity of cinchona alkaloid catalyzed [1,3]-shifts of allylic trichloroacetimidates.
abstract: Density functional theory calculations were used to investigate the [3,3]- and [1,3]-shifts of O-allylic trichloroacetimidates in the presence of cinchona alkaloids. Thermal [1,3]- and [3,3]-rearrangements proceed through concerted pseudopericyclic transition states to give the corresponding rearranged products. [1,3]-Rearrangement is catalyzed via a double S(N)2' mechanism in which syn addition of the nucleophile is exclusively preferred in both steps. The catalyzed mechanism is favored by a 6.3 kcal/mol free energy difference compared to the alternative [3,3]-rearrangement pathway. The fast-reacting enantiomer is predicted to be determined by the availability of the H-bonding interaction between the catalyst and the substrate.
authors.affiliation: Department of Chemistry, Bogaziçi University, Bebek, Istanbul 34342, Turkey.
authors.forename: Nihan
authors.initials: N
authors.lastname: Celebi-Olçüm
authors.forename: Viktorya
authors.initials: V
authors.lastname: Aviyente
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D000081:Acetamides; D000465:Algorithms; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D062845:Chloroacetates; D002930:Cinchona Alkaloids / Q000737:chemistry*; D006860:Hydrogen Bonding; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics; D014238:Trichloroacetic Acid / Q000737:chemistry
chemical_list: D000081:Acetamides; D000498:Allyl Compounds; D062845:Chloroacetates; D002930:Cinchona Alkaloids; D014238:Trichloroacetic Acid; C009528:trichloroacetamide
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