Probing the Mechanism of the Asymmetric Aminolysis of meso-Epoxides Catalyzed by a Proline-Based N,N′-Dioxide-Indium Tris(triflate) Complex

• Published in: Advanced synthesis & catalysis Vol. 354; no. 8; pp. 1509 - 1518
• Main Authors: Gao, Bo, Xie, Mingsheng, Sun, Aimin, Hu, Xiaolei, Ding, Xueqing, Liu, Xiaohua, Lin, Lili, Feng, Xiaoming
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 21.05.2012; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: amino alcohols; aminolysis; Asymmetry; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Applied; Chemistry, Organic; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Kinetics and mechanisms; mechanism analysis; N,N′‐dioxide‐indium tris(triflate) complex; N′-dioxide-indium tris(triflate) complex; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; mechanism analysis; aminolysis; ALDEHYDES; HYDROXYMETHYLATION; amino alcohols; N; AROMATIC-AMINES; ALCOHOLS; MANNICH-TYPE REACTION; KINETIC RESOLUTION; CYCLOADDITIONS; DIELS-ALDER REACTION; BETA-AMINO; N'-dioxide-indium tris(triflate) complex; WATER; Enantioselectivity; Nitrogen heterocycle; Ligand; N,N'-dioxide-indium tris(triflate) complex; Proline; NMR spectrometry; Oxygen heterocycle; Electrospray; Molecular sieve; Asymmetric synthesis; Reaction mechanism; Catalysis; Scanning electron microscopy; Catalytic reaction; Aminoalcohol; Proton transfer; α-Aminoacid; Aminolysis; Aminoacid; Epoxide; Transition state; Enantiomeric excess; Counter ion; Mass spectrometry; Catalyst; Ultraviolet visible spectrometry
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201200142

An exploration of the mechanism of the aminolysis of meso‐epoxides catalyzed by the proline‐based N,N′‐dioxide‐indium tris(triflate) complex was performed using control experiments, UV‐Vis spectroscopy, 1H NMR, electrospray ionization mass spectrometry (ESI‐MS) and scanning electron microscopy (SEM). Control experiments disclosed that the ligand‐to‐indium tris(triflate) ratio, the catalyst loading, the concentration, and the presence of 4 Å MS have dramatic effects on this reaction with regard to both the yield and the enantioselectivity. Combined with control experiments, UV‐Vis spectroscopy, 1H NMR, ESI‐MS and SEM analyses revealed that molecular sieves perform multiple functions in the catalysis. A plausible molecular sieves‐assisted reaction pathway was proposed. In this pathway, molecular sieves perform (i) as desiccant to in situ dry the reaction system, (ii) as proton transfer agent to accelerate the catalysis, and (iii) as counter ion source to preserve the electroneutrality of the transition states. Besides, the generality of the substrate scope was further explored; excellent yields (up to 99%) and enantioselectivities (up to 99% ee) were obtained.