Ligand‐Controlled Chemoselective and Enantioselective Cyclization of Enynes With Aroyl Chlorides
Abstract
ABSTRACT Herein, we report a palladium‐catalyzed, ligand‐controlled approach for the switchable construction of cyclopropane‐fused heterocycles and seven‐membered N‐heterocyclic compounds via the chemoselective cyclization of enynes with aroyl chlorides. Furthermore, enantioselective synthesis of cyclopropane‐fused heterocycles was achieved using a chiral ligand. To highlight the synthetic utility, late‐stage modifications of acid chlorides derived from natural products and pharmaceuticals were demonstrated. DFT calculations reveal that the ligands play an important role in the chemoselective cyclization process by favoring either β‐H or β‐C elimination of the alkyl‐Pd(II) intermediate.
Article Details
Authors (8)
Zhen‐Yu Wang
Shanghai Frontiers Science Center for Drug Target Identification and Delivery National Key Laboratory of Innovative Immunotherapy, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs School of Pharmaceutical Sciences Shanghai Jiao Tong University Shanghai China
Ling‐Xia Zhang
School of Chinese Materia Medica Nanjing University of Chinese Medicine Nanjing Jiangsu China
Yuqing Jiang
Yun‐Qian Zhang
CAS Key Laboratory of Receptor Research State Key Laboratory of Drug Research Shanghai Institute of Materia Medica Chinese Academy of Sciences Shanghai China
Tian‐Qi Gao
School of Chinese Materia Medica Nanjing University of Chinese Medicine Nanjing Jiangsu China
Genping Huang
Department of Chemistry, School of Science
Hui Xu
Hui‐Xiong Dai
Shanghai Frontiers Science Center for Drug Target Identification and Delivery National Key Laboratory of Innovative Immunotherapy, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs School of Pharmaceutical Sciences Shanghai Jiao Tong University Shanghai China