Benzylic C(sp3)-H Azidation: Copper vs Iron Catalysis
Por:
Rentería-Gómez A., Torres-Ochoa R.O., Palamini P., Simonet-Davin R., Wang Q., Waser J., Zhu J.
Publicada:
1 ene 2024
Ahead of Print:
1 mar 2024
Resumen:
The generation of benzylic radicals through hydrogen atom abstraction (HAT) has been a recent research focus and various C(sp3)-H bond functionalization protocols have been developed relying on this elementary step. We report herein copper- and iron-catalyzed C(sp3)-H benzylic azidation reactions using mCPBA and NFSI as oxidant, respectively, and TMSN3 as azide source. The reaction is thought to be initiated via intermolecular abstraction of benzylic hydrogen by the in situ generated heteroatom-centered radicals. The Fe(OTf)3-catalyzed azidation protocol displays good chemoselectivity as it takes place preferentially at the secondary and tertiary benzylic C(sp3)-H bonds over the primary benzylic and tertiary aliphatic carbons. Efforts on the development of catalytic enantioselective processes are also documented. © 2024 The Authors. Helvetica Chimica Acta published by Wiley-VHCA AG, Zurich, Switzerland.
Filiaciones:
Rentería-Gómez A.:
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, Lausanne, 1015, Switzerland
Torres-Ochoa R.O.:
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Ciudad de México, 04510, Mexico
Palamini P.:
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LCSO, BCH 4306, Lausanne, 1015, Switzerland
Simonet-Davin R.:
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LCSO, BCH 4306, Lausanne, 1015, Switzerland
Wang Q.:
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, Lausanne, 1015, Switzerland
Waser J.:
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LCSO, BCH 4306, Lausanne, 1015, Switzerland
Zhu J.:
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, Lausanne, 1015, Switzerland
hybrid, All Open Access; Bronze Open Access
|