Highly regiodivergent copper-catalyzed allylic/propargylic difluoromethylation reactions by employing different ligands are described. When 5,6-dimethyl-1,10-phenanthroline was used as the ligand, exclusively α-diflu...Highly regiodivergent copper-catalyzed allylic/propargylic difluoromethylation reactions by employing different ligands are described. When 5,6-dimethyl-1,10-phenanthroline was used as the ligand, exclusively α-difluoromethylated products were obtained, while γ-selective difluoromethylated products were generated when N-heterocyclic carbene-SIPr was used as the ligand. Likewise, high α- vs. γ-selectivities were achieved in the presence of similar copper catalysts for the reactions of propargyl bromides. Moreover, a copper-catalyzed asymmetric allylic difluoromethylation reaction with moderate to good enantioselectivity by the use of chiral ligands was developed.展开更多
基金The Nationa authors gratefully acknowledge the financial support from Natural Science Foundation of China （21625206, 21632009, 21372247, 21572258, 21572259, 21421002） and the Strategic Priority Research Program of the Chinese Academy of Sciences （XDB20000000） and the Syngenta Ph.D. Fellowship （Y. Gu and C. Lu）.
文摘Highly regiodivergent copper-catalyzed allylic/propargylic difluoromethylation reactions by employing different ligands are described. When 5,6-dimethyl-1,10-phenanthroline was used as the ligand, exclusively α-difluoromethylated products were obtained, while γ-selective difluoromethylated products were generated when N-heterocyclic carbene-SIPr was used as the ligand. Likewise, high α- vs. γ-selectivities were achieved in the presence of similar copper catalysts for the reactions of propargyl bromides. Moreover, a copper-catalyzed asymmetric allylic difluoromethylation reaction with moderate to good enantioselectivity by the use of chiral ligands was developed.
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China （Nos. 21625206, 21632009, 21572258, 21572259, 21421002） and the Strategic Priority Research Program of the Chinese Academy of Sciences （No. XDB20000000） and the Syngenta Ph.D. Fellowship （C. Lu）.
