Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are ...Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are rare.Herein,we report a highly enantioselective nickel-catalyzed alkylation reaction of aldehydes,using readily available alkylborons as nucleophiles.A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields.The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2-symmetric chiral NHC ligand.This protocol features excellent enantiocontrol,mild conditions,and good functional group compatibility.展开更多
N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction o...N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date.Herein,we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals.This methodology exhibits broad substrate scope,good functional group compatibility,and potential synthetic utility by a scale-up reaction,diverse product derivatizations and late-stage functionalization of complex biorelevant molecule.Notably,this transformation selectively allows for the formation of three new chemical bonds(C–O,C–C,and C–N)and one spiro quaternary carbon center across C-C double bonds.展开更多
基金supported by the National Key R&D Program of China(2022YFA1503702,2021YFF0701600)the National Natural Science Foundation of China(22325110,92256303,21821002,22171280)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000)the Program of Shanghai Academic Research Leader(22XD1424900)the CAS Youth Interdisciplinary Team(JCTD-2021-11)and the Ningbo Natural Science Foundation(2022J017).
文摘Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are rare.Herein,we report a highly enantioselective nickel-catalyzed alkylation reaction of aldehydes,using readily available alkylborons as nucleophiles.A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields.The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2-symmetric chiral NHC ligand.This protocol features excellent enantiocontrol,mild conditions,and good functional group compatibility.
基金supported by the National Natural Science Foundation of China(Nos.22101237 and 22171233)Collaborative Fund of Luzhou Government and Southwest Medical University(Nos.2023LZXNYDJ019 and 2024LZXNYDJ050)+1 种基金the Science and Technology Program of Luzhou City(No.2024RCX207)the research fund of Southwest Medical University(Nos.2023QN091 and 2022QN057).
文摘N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date.Herein,we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals.This methodology exhibits broad substrate scope,good functional group compatibility,and potential synthetic utility by a scale-up reaction,diverse product derivatizations and late-stage functionalization of complex biorelevant molecule.Notably,this transformation selectively allows for the formation of three new chemical bonds(C–O,C–C,and C–N)and one spiro quaternary carbon center across C-C double bonds.
