Abbiati Giorgio, Arcadi Antonio, Bianchi Gabriele, Di Giuseppe Sabrina, Marinelli Fabio, Rossi Elisabetta
Istituto di Chimica Organica Alessandro Marchesini, Facoltà di Farmacia, Università degli Studi di Milano, Via Venezian, 21, 20133 Milano, Italy.
J Org Chem. 2003 Sep 5;68(18):6959-66. doi: 10.1021/jo0347260.
A general one-pot synthesis of pyridines 4a-t from the reaction of dialkyl acyclic/cyclic ketones 1a-i, methyl, aryl/heteroaryl ketones 1m-r, and aldehydes bearing alpha-hydrogens 1s,t with propargylamine 2 is described. Gold and copper salts are efficient catalysts for the reaction of ketones with 2. The formation of the pyridines 4 is suggested to proceed through the sequential amination of carbonyl compounds followed by regioselective 6-endo-dig cyclization of the N-propargylenamine (N-propargyldienamine) intermediate 3(5) and aromatization reaction. Whereas the preparation of linear polycyclic pyridine 4i can be carried out by reacting cholestan-3-one 1i with 2, the angular polycyclic pyridine 4j has been obtained starting from cholest-5-en-3-one 1j. Selectivity of the reaction of polycyclic dicarbonyls 1k,l with 2 has also been investigated.
本文描述了一种由无环/环状二烷基酮1a-i、甲基、芳基/杂芳基酮1m-r以及带有α-氢的醛1s,t与炔丙胺2反应一锅法合成吡啶4a-t的通用方法。金盐和铜盐是酮与2反应的有效催化剂。吡啶4的形成被认为是通过羰基化合物的顺序胺化，随后N-炔丙基烯胺（N-炔丙基二烯胺）中间体3(5)进行区域选择性6-内型环化以及芳构化反应。虽然线性多环吡啶4i的制备可以通过胆甾烷-3-酮1i与2反应来进行，但角型多环吡啶4j是从胆甾-5-烯-3-酮1j开始获得的。还研究了多环二羰基化合物1k,l与2反应的选择性。
