Electophilic amination.docVIP

Electrophilic amination is a chemical process involving the formation of a carbon–nitrogen bond through the reaction of a nucleophilic carbanion with an electrophilic source of nitrogen.[1] 亲电胺化(electrophilic amination)是一类重要的有机反应，通过亲电胺化可以使氨基试剂直接与亲核试剂反应，从而直接转化氨基给亲核试剂。但是众所周知氮原子是亲电性很强的原子，含氮原子的试剂，如胺类，都表现出亲核性。还有一些常用的，如硝基，亚硝基等，虽然表现出亲电性，但是反应后还要通过还原才可以得到氨基，而亲电胺化就可以省去这些麻烦。简单说，亲电胺化就是寻找“NH2+”的等价子。下图是一些文献报导的“NH2+”的等价子 (Chem. Rev. 1989, 1947; Synthesis 1991, 327; Tetra. 2004, 8747)。Hydroxylamine-O-sulfonic acid (HOSA, 1); O-(2,4-dinitrophenyl)-hydroxylamine, (DnpONH2, 2); O-(2,4,6-trinitrophenyl)-hydroxylamine, (TnpONH2, 3); O-(diphenylphosphinyl)-hydroxylamine (DppONH2, 4); O-(mesitylenesulfonyl)-hydroxylamine (MtsONH2, 5); O-mesitoylhydroxylamine (MtONH2, 6); O-(p-nitrobenzoyl)hydroxylamine (NbzONH2, 7); Cyclohexanespiro-3-oxaziridine (8); N-Boc-3-(4-cyanophenyl)oxazidine (BCPO, 9),以及氯氨 (chloroamine)。 都是连O上面，显正电性 Contents 1 Introduction 2 Mechanism and stereochemistry 2.1 Prevailing mechanisms 占优势的;主要的;普遍的;盛行的 2.2 Enantioselective variants 变量，转化 3 Scope and limitations 范围;眼界 3.1 Aminating reagents 3.2 Organometallic substrates 4 Comparison with other methods 比较，对照 5 Typical conditions 6 References Introduction Electrophilic amination reactions can be classified as either additions or substitutions. Although the resulting product is not always不总是，不一定 an amine, these reactions are unified使一致的 by the formation of a carbon–nitrogen bond and the use of an electrophilic aminating agent. A wide variety of electrophiles have been used; for substitutions, these are most commonly amines substituted with electron-withdrawing groups: chloramines, hydroxylamines羟胺, hydrazines肼, and oxaziridines, for instance例如. Addition reactions have employed imines亚胺, oximes肟, azides叠氮, azo 偶氮compounds, and others. Mechanism and stereochemistry Prevailing mechanisms A nitrogen bound to both a good electrofuge and a good nucleofuge is known as a nitrenoid (for its resemblance to a nitrene). [2