title: Diastereoselective synthesis of N-(p-tosylsulfonyl)-2-phenylaziridine over a novel magnetically recyclable Cu(II) catalyst accompanied with the N-inversion assessment at DFT.
abstract: An experimental and theoretical study has been carried out on diastereoselective aziridation of styrene over a magnetically recyclable copper(II) catalyst: Cu(acac)2/NH2-T/SiO2@Fe3O4NPs. The turnover number (TON) of our heterogeneous catalyst appears considerably higher than that reported for the homogeneous Cu(acac)2. Successive applications of solid Cu(acac)2/NH2-T/SiO2@Fe3O4NPs have a slight effect on its catalytic activity. Between anticipated cis and trans diastereomeric products, formation of only one is suggested by NMR. Even though, the trans-invertomer appears thermodynamically more stable at B3LYP/AUG-cc-pVTZ//B3LYP/6-31+G+G* level, we propose formation of the kinetically more stable cis-invertomer due to π-stacking between the tosyl group and the phenyl of styrene. The possibility of cis-trans conversion is ruled out by the high energy barrier of > 76.9 kcal/mol probed in toluene, CCl4, C7H16, DMSO, CH3CN, and H2O.
authors.forename: Monireh
authors.initials: M
authors.lastname: Ghavami
authors.forename: Maryam
authors.initials: M
authors.lastname: Koohi
authors.forename: Aliakbar
authors.initials: A
authors.lastname: Ahmadi
authors.forename: Hassan
authors.initials: H
authors.lastname: Zandi
authors.affiliation: Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran. kassaeem@modares.ac.ir.
authors.forename: Mohammad Z
authors.initials: MZ
authors.lastname: Kassaee
mesh_terms: D001388:Aziridines / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D060328:Magnetic Phenomena; D009682:Magnetic Resonance Spectroscopy; D058185:Magnetite Nanoparticles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics; D014105:Tosyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D001388:Aziridines; D058185:Magnetite Nanoparticles; D009942:Organometallic Compounds; D014105:Tosyl Compounds; D003300:Copper