Cobalt(II)-based Metalloradical Activation of 2-(Diazomethyl)pyridines for Radical Transannulation and Cyclopropanation
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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Satyajit Roy1, Sandip Kumar Das1, Buddhadeb Chattopadhyay1
1Division of Molecular Synthesis & Drug Discovery, Centre of Bio-Medical Research (CBMR), SGPGIMS Campus, Raebareli Road, Lucknow, 226014, U.P., India.
Abstract:
A new catalytic method for the denitrogenative transannulation/cyclopropanation of in-situ-generated 2-(diazomethyl)pyridines is described using a cobalt-catalyzed radical-activation mechanism. The method takes advantage of the inherent properties of a CoIII -carbene radical intermediate and is the first report of denitrogenative transannulation/cyclopropanation by a radical-activation mechanism, which is supported by various control experiments. The synthetic benefits of the metalloradical approach are showcased with a short total synthesis of (±)-monomorine.
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