Roveda Jean-Grégoire, Clavette Christian, Hunt Ashley D, Gorelsky Serge I, Whipp Christopher J, Beauchemin André M
Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K1N 6N5.
J Am Chem Soc. 2009 Jul 1;131(25):8740-1. doi: 10.1021/ja902558j.
Benzoic hydrazides (R = Ph), which are remarkably bench and thermally stable reagents (often up to 230 degrees C), afford intramolecular hydroamination products upon heating at high temperatures (120-235 degrees C). A concerted Cope-type hydroamination event, followed by a hydrazide-mediated proton transfer step of the hydrazinium ylide intermediate, is proposed and supported by DFT calculations. In contrast, a simple modification of the reagent structure (R = Ot-Bu or NH(2)) favors the formation of aminocarbonylation products at 200 degrees C, and the latter reaction is shown to be stereospecific.
苯甲酰肼（R = Ph）是非常稳定且热稳定的试剂（通常高达230摄氏度），在高温（120 - 235摄氏度）加热时可得到分子内氢胺化产物。提出了一个协同的科普型氢胺化过程，随后是肼叶立德中间体的酰肼介导的质子转移步骤，并得到了密度泛函理论计算的支持。相比之下，试剂结构的简单修饰（R = Ot-Bu或NH(2)）有利于在200摄氏度下形成氨基羰基化产物，并且后者的反应显示是立体专一性的。
