Sulfilimines as Versatile Gold Nitrene Transfer Reagents: Facile Access to Aza-Heterocyclic Diversity.
Sulfilimines as Versatile Gold Nitrene Transfer Reagents: Facile Access to Aza-Heterocyclic Diversity.
Angew Chem Int Ed Engl. 2019 Jan 02;:
Authors: Tian X, Song L, Rudolph M, Rominger F, Oeser T, Hashmi ASK
Abstract
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 has not been successfully used for gold nitrene transfer before. This work contains an efficient generation of α-imino gold carbenes via 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). This work represents the unique gold-catalyzed reaction between alkynes and sulfur ylides, and also includes the first examples of aza-heterocycle syntheses via 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 using a 1,2-hydride shift onto the α-imino gold carbene and a subsequent Mukaiyama aldol cyclization was discovered.
PMID: 30600592 [PubMed - as supplied by publisher]
Source: Angewandte Chemie - Category: Chemistry Authors: Tian X, Song L, Rudolph M, Rominger F, Oeser T, Hashmi ASK Tags: Angew Chem Int Ed Engl Source Type: research
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