External Reductant-Free Palladium-Catalyzed Reductive Insertion of Isocyanide: Synthesis of Polysubstituted Pyrroles and Its Applications as a Cysteine Probe
External Reductant-Free Palladium-Catalyzed Reductive Insertion of Isocyanide: Synthesis of Polysubstituted Pyrroles and Its Applications as a Cysteine Probe
复制标题
无外部还原剂钯催化异氰化物还原插入：多取代吡咯的合成及其作为半胱氨酸探针的应用
DOI：
10.1021/acs.orglett.9b01220
复制
发表时间：
2019-06-07
期刊：
影响因子：
5.2
通讯作者：
Qiu, Guanyinsheng
中科院分区：
文献类型：
--
作者：
Chen, Dianpeng;Shan, Yingying;Qiu, Guanyinsheng
在这项工作中，通过钯催化还原异氰基插入炔亚胺合成了2-氨基-4-氰基吡咯衍生物，这是一条史无前例的路线。在反应中，不添加外部还原剂，异氰化物既是亚胺化的c1合成子，又是氰化的氰基来源。机理研究表明，该反应涉及[4+1]环加成、异氰化物插入、β-碳消除和基于氢化钯的还原。实现了2-胺-4-氰基吡咯作为半胱氨酸探针检测半胱氨酸的应用。
In this work, an unprecedented route is described for the synthesis of 2-amino-4-cyanopyrrole derivatives via palladium-catalyzed reductive isocyanide insertion of alkynyl imines. In the reactions, no external reductant is added and isocyanide plays a dual role as both a C1 synthon for imidoylation and a cyano source for cyanation. Mechanism studies suggest a [4 + 1] cycloaddition, an isocyanide insertion, beta-carbon elimination, and palladium hydride-based reduction are involved. Moreover, the application of 2-amine-4-cyanopyrroles as a cysteine probe is realized to detect cysteine.