Nitrene Transfer Radical Relay: A Light-Enabled Strategy for Accessing Tetrahydropyridine

Organic Letters, vol. 27, pp. 11866–11871

Abstract

Nitrene transfer reactions represent one of the key reactions to rapidly construct new carbon–nitrogen bonds. Herein, we report on the application of Cu(acac) 2 for the photochemical generation of a copper-bound nitrene intermediate, which is key to access substituted tetrahydropyridines from vinyl cyclopropanes in a (5 + 1) cycloaddition reaction. Experimental and computational studies indicate that the reaction proceeds via the addition of the copper-bound nitrene intermediate to olefin, followed by the ring opening of cyclopropane. The broad applicability of this (5 + 1) cycloaddition is further demonstrated by late-stage functionalization of drug derivatives and downstream transformations of the obtained substituted tetrahydropyridines.

Authors 7

1. Haripriyo Mondal Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

2. Lennard Kloene Aachen Institute of Organic Chemistry

   University of Bayreuth · RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

   University of Bayreuth, Universitätsstraße 30, D-95447 Bayreuth, Germany

3. Sudhir Kumar Hota Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

4. Hufsa Rani

   Indian Institute of Technology Jammu

   Affiliation as printed

   Department of Chemistry

   Indian Institute of Technology Jammu

   Department of Chemistry, Indian Institute of Technology Jammu, Jagti, NH-44, Nagrota Bypass, Jammu 181221, India

5. Claire Empel corresponding Aachen Institute of Organic Chemistry

   University of Bayreuth · RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

   University of Bayreuth, Universitätsstraße 30, D-95447 Bayreuth, Germany

6. Pankaj Chauhan corresponding

   Indian Institute of Technology Jammu

   Affiliation as printed

   Department of Chemistry

   Indian Institute of Technology Jammu

   Department of Chemistry, Indian Institute of Technology Jammu, Jagti, NH-44, Nagrota Bypass, Jammu 181221, India

7. René M. Koenigs corresponding Aachen Institute of Organic Chemistry

   University of Bayreuth · RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

   University of Bayreuth, Universitätsstraße 30, D-95447 Bayreuth, Germany