Sulfur-Nitrogen and Carbon-Nitrogen Bond Formation by Intermolecular Imination and Amidation without Catalyst

• Published in: European Journal of Organic Chemistry Vol. 2012; no. 8; pp. 1554 - 1562
• Main Authors: Ma, Wen Bo, Li, Sheng Nan, Zhou, Zhong Hua, Shen, Heng Shui, Li, Xue, Sun, Qiu, He, Ling, Xue, Ying
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.03.2012; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: C-N coupling; Catalysis; Catalysts: preparations and properties; Chemical reactivity; Chemistry; Chemistry, Organic; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Insertion; Kinetics and mechanisms; Nitrogen heterocycles; Ni­trenes; Organic chemistry; Physical Sciences; Preparations and properties; Reaction mechanisms; Reactivity and mechanisms; S-N coupling; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Nitrenes; SULFOXIMINES; SULFIDES; Insertion; DISSOCIATION ENERGIES; S-N coupling; SULFOXIDES; ALKENES; Nitrogen heterocycles; C-N coupling; ASYMMETRIC AZIRIDINATION; INHIBITORS; Reaction mechanisms; AROMATASE; DERIVATIVES; IRON(II)-MEDIATED NITRENE TRANSFER; Diacetoxyiodobenzene; Nitrogen heterocycle; Nitrene; 1,2,4-Triazole derivative; Oxidant; Amidation; Organic sulfide; Amine; Catalyst-free reaction; Reaction mechanism; Chemical reactivity; Dissociation energy; Olefin; Oxidation potential; Electrochemistry; Imination; Sulfoxide; Catalyst; Ethylenic compound; Hydrogen bond
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201101463

Imination and amidation of sulfides, sulfoxides, and olefins using 4H‐1,2,4‐triazole‐4‐amine as a nitrogen source with PhI(OAc)2 as an oxidant were achieved in moderate to high yields without the addition of a catalyst. The carbon–nitrogen and sulfur–nitrogen bond forming reactivity is consistent with a nitrene insertion mechanism in which the reactivity generally increases with decreasing N–H bond dissociation energy of the nitrogen source and increasing oxidation potential of the oxidant. Imination and amidation of sulfides, sulfoxides, and olefins using 4H‐1,2,4‐triazole‐4‐amine as a nitrogen source with PhI(OAc)2 as an oxidant were achieved in moderate to high yields without the addition of a catalyst. Decreasing N–H bond dissociation energy of the nitrogen source facilitated the nitrene insertion reaction.