铑催化的 N-未取代芳基酮亚胺和炔烃的[3+2]环加成反应合成三级碳胺。

Tertiary carbinamine synthesis by rhodium-catalyzed [3+2] annulation of N-unsubstituted aromatic ketimines and alkynes.

机构信息

Department of Chemistry and Molecular Biology, North Dakota State University, 1231 Albrecht Avenue, P.O. Box 6050, Fargo, ND 58108-6050, USA.

出版信息

Chemistry. 2010 Feb 22;16(8):2619-27. doi: 10.1002/chem.200902814.

DOI:10.1002/chem.200902814

PMID:20077543

Abstract

A convenient and waste-free synthesis of indene-based tertiary carbinamines by rhodium-catalyzed imine/alkyne [3+2] annulation is described. Under the optimized conditions of 0.5-2.5 mol % [{(cod)Rh(OH)}(2)] (cod=1,5-cyclooctadiene) catalyst, 1,3-bis(diphenylphosphanyl)propane (DPPP) ligand, in toluene at 120 degrees C, N-unsubstituted aromatic ketimines and internal alkynes were coupled in a 1:1 ratio to form tertiary 1H-inden-1-amines in good yields and with high selectivities over isoquinoline products. A plausible catalytic cycle involves sequential imine-directed aromatic C-H bond activation, alkyne insertion, and a rare example of intramolecular ketimine insertion into a Rh(I)-alkenyl linkage.

摘要

通过铑催化的亚胺/炔烃[3+2]环加成反应，方便、无浪费地合成了基于茚的三级碳环胺。在优化条件下（[（cod）Rh（OH）]（2）（cod=1,5-环辛二烯）催化剂的 0.5-2.5 mol%、1,3-双（二苯基膦基）丙烷（DPPP）配体、在 120°C 的甲苯中，N-未取代的芳基酮亚胺和内部炔烃以 1:1 的比例偶联，以良好的收率和对异喹啉产物的高选择性形成了三级 1H-茚-1-胺。一个合理的催化循环涉及顺序亚胺导向的芳基 C-H 键活化、炔烃插入和罕见的实例是亚胺插入到 Rh（I）-烯基键中。