金属氮宾与亚胺的复分解反应  

Metal Imide-Mediated Imine Metathesis

作　　者：李林涛[1] 龚华[1] 麻生明[1] 

机构地区：[1]中国科学院

出　　处：《有机化学》2001年第5期398-402,共5页Chinese Journal of Organic Chemistry

摘　　要：综述了近几年来金属氮宾与亚胺的复分解反应.主要集中在锆、钼、钛等过渡金属上.The metal imide-mediated imine methesis (M = Zr, Mo, and Ti) reaction has been reviewed in this paper. (1) Zirconium-mediated imine metathesis Treatment of Cp2Zr(=N-Bu-t)(THF) with 2 equiv. of benzaldehyde phenylimine gave 1 equiv. each of N-tert-butylphenylimine and diazazirconacylobutane. By kinetically stabilizing imidozirconocene complexs via the use of a sterically demanding ligand, or by generating a more thermodynamically stable resting state with addition of diphenylacetylene, Bergman and co-workers have developed transition metal-catalyzed imine metathesis reactions that am mechanistically analogous to olefin metathesis reactions catalyzed by metal carbene complexes. (2) Molybdenum-mediated imine metathesis Bis(imide) complexes (DME)Cl2Mo(=NR)(2) reacted with imines in an imide/imines metathesis to give mixed bis(imide) complexes and new imines. In the presence of 4 mol% of (DME)Cl2Mo(=NR)(2), mixtures of (n-Pr)N = CH-Ph and PhN = CH(t-Bu) underwent catalytic metathesis to form a 1:1:1:1 equilibrium mixture of (n-Pr)N = CHPh, phN = CH( t-Bu), PhN = CHPh, and ( n-Pr)N = CH( t-Bu). A catalytic cycle for imine metathesis was proposed and the nature of the mechanism was discussed in terms of the data obtained with ah of the metatheses. (3) Titanium-mediated imine metathesis Mixtures of [Ti(NBu-t)Cl-2(Py)(3)] and ArN = CHPh gave quantitative conversion to [Ti(NAr)Cl-2 (Py)(3)] and t-BuN = CHPh, the products of Ti = NBu-t/C = NAr transition metal imide/organic imine metathesis; examination of the kinetics shaved that the rate-limiting step for this process is zero order with metal imides; demonstating that these reactions do not involve metal particiption in the rate-limiting step. The reactions of the titanium imido complexs [Ti(NR)Cl-2(Py)(3)] with alpha -diimines of the type ArNC(R-1)C(R-1)NAr are critically dependent on the nature of both the titanium-imido complexes and the substitutent in diimines.

关 键 词：金属氮宾 亚胺 复分解反应 碳氮双键 锆 钼 钛氮宾 

分 类 号：O623.7[理学—有机化学]