Au SM, Huang JS, Che CM, Yu WY
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.
J Org Chem. 2000 Nov 17;65(23):7858-64. doi: 10.1021/jo000881s.
Selective amidation of simple hydrocarbons with pre-isolated and in-situ formed iminoiodanes catalyzed by ruthenium complexes [Ru(III)(Me(3)tacn)(CF(3)CO(2))(3).H(2)O] (2b, Me(3)tacn = N,N', N"-trimethyl-1,4,7-triazacyclononane) and cis-[Ru(II)(6, 6'-Cl(2)bpy)(2)Cl(2)] (3, 6,6'-Cl(2)bpy = 6,6'-dichloro-2, 2'-bipyridine) was investigated. With PhI=NTs as nitrogen source, both catalysts efficiently promote the amidation of adamantane, cyclohexene, ethylbenzene, cumene, indan, tetralin, and diphenylmethane to afford N-substituted sulfonamides in 80-93% yields with high selectivity. Competitive amidations of para-substituted ethylbenzenes and kinetic isotope effect for the amidation of cyclohexene/cyclohexene-d(10) suggest that the amidation processes probably proceed via the hydrogen abstraction by a reactive Ru=NTs species to form a carboradical intermediate. The amidation with PhI(OAc)(2)/TsNH(2) gave results comparable to those obtained with PhI=NTs. Extension of the "PhI(OAc)(2)/TsNH(2) + catalyst 2b or 3" protocol to MeSO(2)NH(2) and PhCONH(2) with ethylbenzene as substrate produced the corresponding N-substituted amides in up to 89% yield.
研究了钌配合物[Ru(III)(Me(3)tacn)(CF(3)CO(2))(3).H(2)O]（2b，Me(3)tacn = N,N',N"-三甲基-1,4,7-三氮杂环壬烷）和顺式-[Ru(II)(6,6'-Cl(2)bpy)(2)Cl(2)]（3，6,6'-Cl(2)bpy = 6,6'-二氯-2,2'-联吡啶）催化的简单烃与预分离和原位形成的亚氨基碘烷的选择性酰胺化反应。以PhI=NTs作为氮源，两种催化剂均能有效促进金刚烷、环己烯、乙苯、异丙苯、茚满、四氢化萘和二苯甲烷的酰胺化反应，以80-93%的产率和高选择性得到N-取代磺酰胺。对对位取代乙苯的竞争性酰胺化反应以及环己烯/环己烯-d(10)酰胺化反应的动力学同位素效应表明，酰胺化过程可能是通过一个活性Ru=NTs物种夺取氢形成碳自由基中间体进行的。用PhI(OAc)(2)/TsNH(2)进行的酰胺化反应结果与用PhI=NTs得到的结果相当。将“PhI(OAc)(2)/TsNH(2)+催化剂2b或3”的方法扩展到以乙苯为底物的MeSO(2)NH(2)和PhCONH(2)，能以高达89%的产率得到相应的N-取代酰胺。
