Dual Photoredox/Copper Catalysis for the Remote C(sp3)−H Functionalization of Alcohols and Alkyl Halides by N-Alkoxypyridinium Salts
Dr. Xu Bao
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland
Search for more papers by this authorDr. Qian Wang
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Dr. Jieping Zhu
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland
Search for more papers by this authorDr. Xu Bao
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland
Search for more papers by this authorDr. Qian Wang
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Dr. Jieping Zhu
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland
Search for more papers by this authorGraphical Abstract
Be selective: δ-Azido, δ-cyano, and δ-thiocyanato alcohols were obtained in high yields from N-alkoxypyridinium salts under mild dual photoredox/copper catalysis. A catalytic enantioselective δ-cyanation protocol in the presence of a chiral bisoxazoline ligand was also developed.
Abstract
Under mild dual photoredox/copper catalysis, the reaction of N-alkoxypyridinium salts with readily available silyl reagents (TMSN3, TMSCN, TMSNCS) afforded δ-azido, δ-cyano, and δ-thiocyanato alcohols in high yields. The reaction went through a domino process involving alkoxy radical generation, 1,5-hydrogen atom transfer (1,5-HAT) and copper-catalyzed functionalization of the resulting C-centered radical. Conditions for catalytic enantioselective δ-C(sp3)−H cyanation were also documented.
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