The enantioselective separation of racemate,particularly those containing C(sp^(3))-H bonds knowns for their high bond dissociation energies and significant polarity,presents a significant challenge in pharmaceutical ...The enantioselective separation of racemate,particularly those containing C(sp^(3))-H bonds knowns for their high bond dissociation energies and significant polarity,presents a significant challenge in pharmaceutical synthesis.Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer(HAT)methodologies,marking a notable trend in synthesis of chiral molecules.This technique uses the excitation of a catalyst to activate substrates,enabling the selective isomerization of chiral centers containing C(sp^(3))configurations.This process distinctively facilitates the direct activation of the C(sp^(3))-H bond in targeted reagents.This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp^(3))-H centers,capable of undergoing deracemization through two primary HAT mechanisms:direct and indirect pathways.From the perspective of synthetic organic chemistry,this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at theα-position adjacent to the C(sp^(3))chiral center.Moreover,it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations.The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.展开更多
Chiralα-substituted 1,3-dihydroisobenzofurans are key scaffolds in a number of bioactive natural products and synthetic pharmaceuticals.However,catalytic asymmetric approaches have been rarely developed.Here,a redox ...Chiralα-substituted 1,3-dihydroisobenzofurans are key scaffolds in a number of bioactive natural products and synthetic pharmaceuticals.However,catalytic asymmetric approaches have been rarely developed.Here,a redox deracemization technology is adopted to address the catalytic asymmetric synthesis.A broad range ofα-aryl substituted 1,3-dihydroisobenzofurans are effectively deracemized in high efficiency with excellent ee.α-Alkynyl substituted ethers were also compatible with the deracemization technology.展开更多
Chirality is a universal characteristic of life and the material world,with irreplaceable value in drug development and green synthesis[1].At present,enantioselective transformations primarily rely on two methods,whic...Chirality is a universal characteristic of life and the material world,with irreplaceable value in drug development and green synthesis[1].At present,enantioselective transformations primarily rely on two methods,which are asymmetric synthesis using chiral catalysts or reagents and kinetic resolution depending on enantiomer recognition ability.展开更多
The concurrent implementation of cascade reactions that combine biocatalysis and chemocatalysis is a challenging undertaking.Electrocatalysis provides versatile catalytic abilities and allows for mild reaction conditi...The concurrent implementation of cascade reactions that combine biocatalysis and chemocatalysis is a challenging undertaking.Electrocatalysis provides versatile catalytic abilities and allows for mild reaction conditions,offering the potential for designing concurrent chemoenzymatic cascade reactions.The research on bioelectrocatalysis has primarily concentrated on utilizing electrocatalysis to achieve cofactor regeneration of enzymes.In contrast with previous reports,herein,we developed a deracemization strategy involving the concurrent combination of biocatalytic reduction and anodic oxidation in an undivided cell to achieve chiral sulfoxides,demonstrating the good compatibility.We anticipate this study will offer an alternative pathway for the design of the cascade reaction combined with electrocatalysis and biocatalysis.展开更多
基金the National Natural Science Foundation of China(No.22072020)the Science Foundation of the Fujian Province(Nos.2022HZ027004,2022L3082,2021L3003,and 2019 J01203).
文摘The enantioselective separation of racemate,particularly those containing C(sp^(3))-H bonds knowns for their high bond dissociation energies and significant polarity,presents a significant challenge in pharmaceutical synthesis.Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer(HAT)methodologies,marking a notable trend in synthesis of chiral molecules.This technique uses the excitation of a catalyst to activate substrates,enabling the selective isomerization of chiral centers containing C(sp^(3))configurations.This process distinctively facilitates the direct activation of the C(sp^(3))-H bond in targeted reagents.This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp^(3))-H centers,capable of undergoing deracemization through two primary HAT mechanisms:direct and indirect pathways.From the perspective of synthetic organic chemistry,this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at theα-position adjacent to the C(sp^(3))chiral center.Moreover,it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations.The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
基金financial supported by the National Natural Science Foundation of China(Nos.21971148)Shenzhen Special Funds(No.JCYJ20190807093805572)。
文摘Chiralα-substituted 1,3-dihydroisobenzofurans are key scaffolds in a number of bioactive natural products and synthetic pharmaceuticals.However,catalytic asymmetric approaches have been rarely developed.Here,a redox deracemization technology is adopted to address the catalytic asymmetric synthesis.A broad range ofα-aryl substituted 1,3-dihydroisobenzofurans are effectively deracemized in high efficiency with excellent ee.α-Alkynyl substituted ethers were also compatible with the deracemization technology.
基金supported by the National Natural Science Foundation of China(22271227 and 22471205)Guangdong Basic and Applied Basic Research Foundation(2024A1515011322)+2 种基金the China Postdoctoral Science Foundation(2024M752457)the Postdoctoral Fellowship Program(Grade B)of China Postdoctoral Science Foundation(GZB20240566)Wuhan University and Hubei University for their support of this research.
文摘Chirality is a universal characteristic of life and the material world,with irreplaceable value in drug development and green synthesis[1].At present,enantioselective transformations primarily rely on two methods,which are asymmetric synthesis using chiral catalysts or reagents and kinetic resolution depending on enantiomer recognition ability.
基金funded by the National Natural Science Foundation of China(Nos.22322705,22171243,22301276)National Key Research and Development Program of China(No.2021YFC2102000)+1 种基金Zhejiang Provincial Natural Science Foundation of China(No.LQ24B020009)Scientific Research Starting Foundation of Zhejiang University of Technology(No.2020105009029).
文摘The concurrent implementation of cascade reactions that combine biocatalysis and chemocatalysis is a challenging undertaking.Electrocatalysis provides versatile catalytic abilities and allows for mild reaction conditions,offering the potential for designing concurrent chemoenzymatic cascade reactions.The research on bioelectrocatalysis has primarily concentrated on utilizing electrocatalysis to achieve cofactor regeneration of enzymes.In contrast with previous reports,herein,we developed a deracemization strategy involving the concurrent combination of biocatalytic reduction and anodic oxidation in an undivided cell to achieve chiral sulfoxides,demonstrating the good compatibility.We anticipate this study will offer an alternative pathway for the design of the cascade reaction combined with electrocatalysis and biocatalysis.
