铜催化的氧化条件下的 Huisgen 1,3-偶极环加成反应：4-酰基-1-取代-1,2,3-三唑的聚合物辅助组装。

Copper-catalyzed Huisgen 1,3-dipolar cycloaddition under oxidative conditions: polymer-assisted assembly of 4-acyl-1-substituted-1,2,3-triazoles.

机构信息

Center for Research in Biological Chemistry and Molecular Materials (CIQUS), University of Santiago de Compostela, 15782 Santiago de Compostela, Spain.

出版信息

J Org Chem. 2013 Jul 5;78(13):6540-9. doi: 10.1021/jo400800j. Epub 2013 Jun 14.

DOI:10.1021/jo400800j

PMID:23738944

Abstract

We herein document the first example of a reliable copper-catalyzed Huisgen 1,3-dipolar cycloaddition under oxidative conditions. The combined use of two polymer-supported reagents (polystyrene-1,5,7-triazabicyclo[4,4,0]dec-5-ene/Cu and polystyrene-2-iodoxybenzamide) overcomes the thermodynamic instability of copper(I) species toward oxidation, enabling the reliable Cu-catalyzed Huisgen 1,3-dipolar cycloadditions in the presence of an oxidant agent. This polymer-assisted pathway, not feasible under conventional homogeneous conditions, provides a direct assembly of 4-acyl-1-substituted-1,2,3-triazoles, contributing to expand the reliability and scope of Cu(I)-catalyzed alkyne-azide cycloaddition.

摘要

我们在此记录了首例在氧化条件下可靠的铜催化的 Huisgen 1,3-偶极环加成反应。两种聚合物负载试剂（聚苯乙烯-1,5,7-三氮杂双环[4.4.0]癸-5-烯/Cu 和聚苯乙烯-2-碘代苯甲酰胺）的联合使用克服了铜（I）物种对氧化的热力学不稳定性，从而在氧化剂存在的情况下实现了可靠的铜催化的 Huisgen 1,3-偶极环加成反应。这种在传统均相条件下不可行的聚合物辅助途径提供了 4-酰基-1-取代-1,2,3-三唑的直接组装，有助于扩大 Cu(I)-催化的炔烃-叠氮化物环加成的可靠性和范围。