Institut für Organische Chemie, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589, Saudi Arabia.
Angew Chem Int Ed Engl. 2019 Mar 11;58(11):3589-3593. doi: 10.1002/anie.201812002. Epub 2019 Jan 31.
We herein report the unprecedented synthesis of diverse biologically important aza-heterocycles by employing sulfilimines as nitrene transfer reagents. This class of sulfur-based aza-ylides had not been successfully used for gold nitrene transfer before. This work contains an efficient generation of α-imino gold carbenes by N-S cleavage of sulfilimines. These gold carbenes undergo C-H insertion, cyclopropanation, and nucleophilic attack to form indoles (44 examples), 3-azabicyclo[3.1.0]hexan-2-imines (24 examples), and imidazoles (3 examples). Our study represents a unique gold-catalyzed reaction between alkynes and sulfur ylides, and also includes the first aza-heterocycle synthesis that proceeds by intermolecular nitrene transfer followed by cyclopropanation of the α-imino gold carbenes. Moreover, an unexpected synthesis of 4-acylquinolines (3 examples) from 2-acylphenyl sulfilimines and propargylic silyl ether derivatives by a 1,2-hydride shift onto the α-imino gold carbene and a subsequent Mukaiyama aldol cyclization was discovered.
我们在此报告了一种前所未有的通过亚磺酰胺作为氮烯转移试剂合成多种具有生物重要性的氮杂杂环的方法。这类基于硫的氮杂叶立德以前从未成功用于金氮烯转移。这项工作通过亚磺酰胺的 N-S 裂解有效地生成了α-亚氨基金卡宾。这些金卡宾经历 C-H 插入、环丙烷化和亲核攻击，形成吲哚（44 个实例）、3-氮杂双环[3.1.0]己-2-亚胺（24 个实例）和咪唑（3 个实例）。我们的研究代表了炔烃和硫叶立德之间的一种独特的金催化反应，还包括首例通过氮烯转移后α-亚氨基金卡宾的环丙烷化进行的氮杂杂环合成。此外，还发现了 2-酰基苯基亚磺酰胺和丙炔基硅醚衍生物通过α-亚氨基金卡宾上的 1,2-氢迁移和随后的 Mukaiyama 缩合环化生成 4-酰基喹啉（3 个实例）的意外合成。
