Tunable, Chemoselective Amination via Silver Catalysis
摘要:
Organic N-containing compounds, including amines, are essential components of many biologically and pharmaceutically important molecules. One strategy for introducing nitrogen into substrates with multiple reactive bonds is to insert a monovalent N fragment (nitrene or nitrenoid) into a C H bond or add it directly to a C=C bond. However, it has been challenging to develop well-defined catalysts capable of promoting predictable and chemoselective aminations solely through reagent control. Herein, we report remarkable chemoselective aminations that employ a single metal (Ag) and a single ligand (phenanthroline) to promote either aziridination or C H insertion by manipulating the coordination geometry of the active catalysts.
BICYCLIC METHYLENE AZIRIDINES AND REACTIONS THEREOF
申请人:Wisconsin Alumni Research Foundation
公开号:US20160075668A1
公开(公告)日:2016-03-17
The oxidative functionalization of olefins is a common method for the formation of vicinal carbon-heteroatom bonds. However, oxidative methods to transform allenes into synthetic motifs containing three contiguous carbon-heteroatom bonds are much less developed. The use of bicyclic methylene aziridines (MAs), prepared via intramolecular allene aziridination, as scaffolds for functionalization of all three allene carbons, among other reactions, is described herein.
作者:Jared W. Rigoli、Cale D. Weatherly、Juliet M. Alderson、Brian T. Vo、Jennifer M. Schomaker
DOI:10.1021/ja406654y
日期:2013.11.20
Organic N-containing compounds, including amines, are essential components of many biologically and pharmaceutically important molecules. One strategy for introducing nitrogen into substrates with multiple reactive bonds is to insert a monovalent N fragment (nitrene or nitrenoid) into a C H bond or add it directly to a C=C bond. However, it has been challenging to develop well-defined catalysts capable of promoting predictable and chemoselective aminations solely through reagent control. Herein, we report remarkable chemoselective aminations that employ a single metal (Ag) and a single ligand (phenanthroline) to promote either aziridination or C H insertion by manipulating the coordination geometry of the active catalysts.