Chiral pyridyl alcohols are a type of synthetically versatile building block for natural products,functional materials and bioactive molecules.Herein,a highly efficient Ir/f-amphox-catalyzed asymmetric hydrogenation o...Chiral pyridyl alcohols are a type of synthetically versatile building block for natural products,functional materials and bioactive molecules.Herein,a highly efficient Ir/f-amphox-catalyzed asymmetric hydrogenation of 1-(pyridin-2-yl)ketone derivatives to access chiral pyridyl alcohols was reported.The reaction proceeds smoothly under mild conditions,delivering excellent yields and enantioselectivities(up to>99%ee,turnover number(TON)up to 2000).A broad range of pyridyl alkyl and aryl ketones were successfully transformed,demonstrating the generality and synthetic utility of this methodology.展开更多
A transition-metal-and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source.A broad array of readily accessible ...A transition-metal-and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source.A broad array of readily accessible N-(pyridyl)amides could be converted into the products featuring a diverse set of functional groups.The sustainable methodology was successfully applied to the late-stage functionalization of natural products and drugs.展开更多
A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-d...A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-diphenylphosphinyl-1-naphthyl bromides.The Pd-catalysis plays dual roles in the formation of both axial C–C bond and isoquinoline ring.This de novo synthetic strategy features good functional group tolerance,high yields and easy scale-up,providing Quinap derivatives with substitution patterns that could not be obtained using coupling reactions.Chiral ligands 7 and 12 can be readily prepared by transformation of the resulting Quinap oxide to their BINOL esters,and have been proven to be superb chiral ligands for the copper-catalyzed enantioselective A^(3)-coupling and alkynylation of quinoline reactions.In general,the enantioselectivies obtained using ligands 7 and 12 are excellent,and the ee values are higher than those using Quinap as ligand,even three times higher in some cases.Mechanism studies revealed that a monomeric copper(Ⅰ)complex bearing a single chiral ligand was formed and served as the catalytically active species.展开更多
文摘Chiral pyridyl alcohols are a type of synthetically versatile building block for natural products,functional materials and bioactive molecules.Herein,a highly efficient Ir/f-amphox-catalyzed asymmetric hydrogenation of 1-(pyridin-2-yl)ketone derivatives to access chiral pyridyl alcohols was reported.The reaction proceeds smoothly under mild conditions,delivering excellent yields and enantioselectivities(up to>99%ee,turnover number(TON)up to 2000).A broad range of pyridyl alkyl and aryl ketones were successfully transformed,demonstrating the generality and synthetic utility of this methodology.
基金financial support from the National Natural Science Foundation of China(No.82003585)the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.24HASTIT069)+5 种基金the Technical Innovation Team of Henan Normal University(No.2022TD03)the Special Project for Fundamental Research in University of Henan Province(No.23ZX009)the Henan Science and Technology Program(No.232102310364)the Key Project of Henan Educational Committee(No.22A150041)Excellent Youth Foundation of Henan Scientific Committee(No.222300420012)the Young Core Instructor Training Program of Xinyang Agriculture and Forestry University(2023)。
文摘A transition-metal-and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source.A broad array of readily accessible N-(pyridyl)amides could be converted into the products featuring a diverse set of functional groups.The sustainable methodology was successfully applied to the late-stage functionalization of natural products and drugs.
基金Financial support from the National Natural Science Foundation of China(No.22171168)Excellent Youth Foundation of Henan Scientific Committee(No.222300420012)Taishan Scholar Program of Shandong Province is gratefully acknowledged。
文摘A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-diphenylphosphinyl-1-naphthyl bromides.The Pd-catalysis plays dual roles in the formation of both axial C–C bond and isoquinoline ring.This de novo synthetic strategy features good functional group tolerance,high yields and easy scale-up,providing Quinap derivatives with substitution patterns that could not be obtained using coupling reactions.Chiral ligands 7 and 12 can be readily prepared by transformation of the resulting Quinap oxide to their BINOL esters,and have been proven to be superb chiral ligands for the copper-catalyzed enantioselective A^(3)-coupling and alkynylation of quinoline reactions.In general,the enantioselectivies obtained using ligands 7 and 12 are excellent,and the ee values are higher than those using Quinap as ligand,even three times higher in some cases.Mechanism studies revealed that a monomeric copper(Ⅰ)complex bearing a single chiral ligand was formed and served as the catalytically active species.
