Merck Center for Catalysis at Princeton University , Princeton, New Jersey 08544, United States.
J Am Chem Soc. 2013 Oct 30;135(43):16074-7. doi: 10.1021/ja4096472. Epub 2013 Oct 16.
The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino-substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst is reconstituted. The practical value of this transformation is highlighted through one-step syntheses of two high-profile pharmaceutical agents, Plavix and amfepramone.
酮类、酯类和醛类的直接α-胺化反应已经通过铜催化来实现。在催化量的二价溴化铜存在下,各种羰基和胺类底物通过片段偶联反应生成具有合成用途的α-氨基取代基。该转化被认为是通过催化生成的α-溴代羰基物种进行的;然后,胺对溴化物的亲核取代反应生成α-氨基羰基加合物,同时催化剂得到再生。该转化的实际价值通过两个高知名度的药物(Plavix 和安非拉酮)的一步合成得到了突出体现。