title: A theoretical study of rhodium(I) catalyzed carbonylative ring expansion of aziridines to beta-lactams: crucial activation of the breaking C-N bond by hyperconjugation.
abstract: The regioselectivity and enantiospecificity of the [Rh(CO)2Cl]2-catalyzed carbonylative ring expansions of N-tert-butyl-2-phenylaziridine to yield 2-azetidinone and the lack of reactivity of N-tert-butyl-2-methylaziridine along this process were investigated at the B3LYP/6-31G(d) (LANL2DZ for Rh) theory level taking into account solvent effects. According to our results, the regioselectivity in the ring expansion of N-tert-butyl-2-phenylaziridine and the unreactivity of N-tert-butyl-2-methylaziridine experimentally observed are determined by the different degree of activation of the breaking C-N bond in the initial aziridine-Rh(CO)2Cl complex due to its hyperconjugation interaction with the substituent on the carbon atom. When a phenyl substituent is present its hyperconjugation interaction with the C(alpha)-N bond facilitates the insertion of the metal atom into this bond. On the other hand, when the substituent is a methyl group, a larger stability of the initial complex along with a lower stabilization through hyperconjugation of the TS for insertion of the Rh atom into the C(alpha)-N bond make the ring expansion of N-tert-butyl-2-methylaziridine unviable. The enantiospecificity experimentally observed is also reproduced by our calculations given that the stereogenic center is never perturbed to change its configuration.
authors.affiliation: Departamento de Química Física y Analítica, Universidad de Oviedo, Julian Clavería, 8, E-33006 Oviedo, Spain.
authors.forename: Diego
authors.initials: D
authors.lastname: Ardura
authors.forename: Ramón
authors.initials: R
authors.lastname: López
authors.forename: Tomas L
authors.initials: TL
authors.lastname: Sordo
mesh_terms: D001388:Aziridines / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D047090:beta-Lactams / Q000737:chemistry*
chemical_list: D001388:Aziridines; D047090:beta-Lactams; D002244:Carbon; D012238:Rhodium; D009584:Nitrogen