Developed is an efficient three-component [3 + 2 + 1] cycloaddition of simple alkenes with two C—H substrates via oxidative dicarbofunctionalization/cyclization sequence. The copper-catalyzed reaction involves the fo...Developed is an efficient three-component [3 + 2 + 1] cycloaddition of simple alkenes with two C—H substrates via oxidative dicarbofunctionalization/cyclization sequence. The copper-catalyzed reaction involves the formation of two C—C bonds and one C—O bond through the cleavage of three C—H bonds in a single operation. The method has an excellent functional group tolerance, and features a broad substrate scope, affording a variety of functionalized chromenes in good yields.展开更多
Lignans have been established as a privileged scaffold in drug discovery,particularly in anticancer and antioxidant properties.Concise and efficient construction of lignans and their derivatives in a single operation ...Lignans have been established as a privileged scaffold in drug discovery,particularly in anticancer and antioxidant properties.Concise and efficient construction of lignans and their derivatives in a single operation holds great medicinal significance for structure-activity relationship studies yet remains challenging.Drawing inspiration from the biosynthesis of lignans,we present a general,high-step-economy palladium-catalyzed reaction that converts simple chemical feedstocks into dehydrodibenzylbutyrolactone lignans through the in-situ construction and coupling of two phenylpropanoid molecules.The diversity of organoboronic acids and the editability of enyne provide a powerful platform for the rapid construction of lignan libraries,featuring 82 lignans analogs,collective syntheses of 10 distinct lignan skeletons,and 13 hybrid molecules combining pharmacophore fragments with drug and derivatives.The subtle combination of phosphine ligands with quinones for switching chemoselectivity is vital to the success of this protocol.展开更多
Highly enantioselective and diastereoselective 1,2-diarylation and 1,2-arylalkynylation of trisubstituted alkenes are reported via the palladium-catalyzed Heck/Suzuki or Heck/Sonogashira domino sequence.These alkenes ...Highly enantioselective and diastereoselective 1,2-diarylation and 1,2-arylalkynylation of trisubstituted alkenes are reported via the palladium-catalyzed Heck/Suzuki or Heck/Sonogashira domino sequence.These alkenes represent an extension of enantioselective dicarbofunctionalization from terminal alkenes to trisubstituted ones based on anionic capture of the secondary alkyl-Pd intermediate.展开更多
Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s)that often change the physicochemical and biological properties of organic mo...Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s)that often change the physicochemical and biological properties of organic molecules.Transition-metal-mediated cross-electrophile coupling between carbon electrophiles and fluoroalkyl electrophiles has emerged as a straightforward and efficient route for the synthesis of a wide range of fluoroalkylated compounds because of its synthetic convenience without the tedious synthesis of organometallic reagents.Moreover,alkenes or alkynes-involved three-component cross-electrophile couplings provide rapid and effective access to carbonfunctionalized fluoroalkylated alkanes and alkenes.Herein,we comprehensively summarize the transition-metal-mediated reductive fluoroalkylation of diverse carbon electrophiles through a historical perspective,including trifluoromethylation,difluoroalkylation,monofluoroalkylation,and so on.Different transition metals(Cu,Ni,etc.)and strategies are discussed,in which nickel-catalyzed reductive fluoroalkylation reactions represent an attractive and efficient synthetic route to site-selectively access organofluorine compounds.展开更多
The facile construction of chiral quaternaryα-alkenylated pyrrolidinones is a long-term challenge in organic synthesis.The asymmetric difunctionalization of 1,3-dienes represents the most compelling tool for assembli...The facile construction of chiral quaternaryα-alkenylated pyrrolidinones is a long-term challenge in organic synthesis.The asymmetric difunctionalization of 1,3-dienes represents the most compelling tool for assembling alkenylated compounds by regioselective 1,2-or 1,4-difunctionalization.Nevertheless,the manipulation of unactivated 1,3-dienes to forge the quarternary stereogenic center still remains largely underdeveloped.Herein,we disclose a nickelcatalyzed asymmetric 1,4-arylcarbamoylation of unactivated 1,3-dienes tethered on carbamoyl fluoride with readily available arylboronic acids,providing rapid access to the enantioenrichedα-alkenylated pyrrolidinones bearing the quaternary stereogenic center in high yields with broad functional group tolerance.Moreover,this chiral ligand-controlled asymmetric transformation overcomes the intrinsic substrate control with a preexisting chiral center.展开更多
Herein we report a nickel-catalyzed asymmetric two-component reductive aryl-acylation and arylcarbamoylation of aryl-iodide-tethered unactivated alkenes,which utilize ortho-pyridinyl esters and isocyanates as the elec...Herein we report a nickel-catalyzed asymmetric two-component reductive aryl-acylation and arylcarbamoylation of aryl-iodide-tethered unactivated alkenes,which utilize ortho-pyridinyl esters and isocyanates as the electrophilic acyl sources,respectively.Under the catalysis of a nickel–pyrox complex with zinc powder as the reductant,a variety of chiral indanes,indolines,and dihydrobenzofurans bearing a quaternary stereogenic center were prepared in moderate to high efficiency and good to excellent enantioselectivities.The utility of this method is demonstrated by various simple derivatizations of the attached carbonyl group,particularly the sequential benzylic oxidation and pinacol coupling,which provide a concise entry to the benzene-fused bicyclic bridged ring framework containing three challenging tetrasubstituted stereocenters in high stereocontrol.展开更多
基金the funding support of the National Natural Science Foundation of China(Nos.92156008,22161142016,21971148)the China Postdoctoral Science Foundation(No.2019M662321)the Postdoctoral Innovation Project of Shandong Province(No.202001003).
文摘Developed is an efficient three-component [3 + 2 + 1] cycloaddition of simple alkenes with two C—H substrates via oxidative dicarbofunctionalization/cyclization sequence. The copper-catalyzed reaction involves the formation of two C—C bonds and one C—O bond through the cleavage of three C—H bonds in a single operation. The method has an excellent functional group tolerance, and features a broad substrate scope, affording a variety of functionalized chromenes in good yields.
基金Financial support was provided by the State Key Laboratory of Pulp and Paper Engineering(No.2022PY01)the National Natural Science Foundation of China(Nos.22231002 and 21871095)the Key-Area Research and Development Program of Guangdong Province(No.2020B010188001)。
文摘Lignans have been established as a privileged scaffold in drug discovery,particularly in anticancer and antioxidant properties.Concise and efficient construction of lignans and their derivatives in a single operation holds great medicinal significance for structure-activity relationship studies yet remains challenging.Drawing inspiration from the biosynthesis of lignans,we present a general,high-step-economy palladium-catalyzed reaction that converts simple chemical feedstocks into dehydrodibenzylbutyrolactone lignans through the in-situ construction and coupling of two phenylpropanoid molecules.The diversity of organoboronic acids and the editability of enyne provide a powerful platform for the rapid construction of lignan libraries,featuring 82 lignans analogs,collective syntheses of 10 distinct lignan skeletons,and 13 hybrid molecules combining pharmacophore fragments with drug and derivatives.The subtle combination of phosphine ligands with quinones for switching chemoselectivity is vital to the success of this protocol.
基金support from the National Natural Science Foundation of China(nos.21702184,21772175,and 91956117).
文摘Highly enantioselective and diastereoselective 1,2-diarylation and 1,2-arylalkynylation of trisubstituted alkenes are reported via the palladium-catalyzed Heck/Suzuki or Heck/Sonogashira domino sequence.These alkenes represent an extension of enantioselective dicarbofunctionalization from terminal alkenes to trisubstituted ones based on anionic capture of the secondary alkyl-Pd intermediate.
基金supported by the National Natural Science Foundation of China(21931013,21991122)the National Key R&D Program of China(2021YFF0701700)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000)the Science and Technology Commission of Shanghai Municipality(22JC1403500,21XD1404400).
文摘Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s)that often change the physicochemical and biological properties of organic molecules.Transition-metal-mediated cross-electrophile coupling between carbon electrophiles and fluoroalkyl electrophiles has emerged as a straightforward and efficient route for the synthesis of a wide range of fluoroalkylated compounds because of its synthetic convenience without the tedious synthesis of organometallic reagents.Moreover,alkenes or alkynes-involved three-component cross-electrophile couplings provide rapid and effective access to carbonfunctionalized fluoroalkylated alkanes and alkenes.Herein,we comprehensively summarize the transition-metal-mediated reductive fluoroalkylation of diverse carbon electrophiles through a historical perspective,including trifluoromethylation,difluoroalkylation,monofluoroalkylation,and so on.Different transition metals(Cu,Ni,etc.)and strategies are discussed,in which nickel-catalyzed reductive fluoroalkylation reactions represent an attractive and efficient synthetic route to site-selectively access organofluorine compounds.
基金supported by National Natural Science Foundation of China(grant no.22171079)the Natural Science Foundation of Shanghai(grant no.21ZR1480400)+3 种基金the Shanghai Rising-Star Program(grant no.20QA1402300)the Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03)the Program of Introducing Talents of Discipline to Universities(grant no.B16017)the Fundamental Research Funds for the Central Universities and the China Postdoctoral Science Foundation(grant no.2021M701197).
文摘The facile construction of chiral quaternaryα-alkenylated pyrrolidinones is a long-term challenge in organic synthesis.The asymmetric difunctionalization of 1,3-dienes represents the most compelling tool for assembling alkenylated compounds by regioselective 1,2-or 1,4-difunctionalization.Nevertheless,the manipulation of unactivated 1,3-dienes to forge the quarternary stereogenic center still remains largely underdeveloped.Herein,we disclose a nickelcatalyzed asymmetric 1,4-arylcarbamoylation of unactivated 1,3-dienes tethered on carbamoyl fluoride with readily available arylboronic acids,providing rapid access to the enantioenrichedα-alkenylated pyrrolidinones bearing the quaternary stereogenic center in high yields with broad functional group tolerance.Moreover,this chiral ligand-controlled asymmetric transformation overcomes the intrinsic substrate control with a preexisting chiral center.
基金supported by start-up funds from the Young Scholar 1000 Talents Planthe National Natural Science Foundation of China(21772183 and 22071230)+2 种基金the Fundamental Research Funds for the Central Universities(WK2060190086)the Project Funded by China Postdoctoral Science Foundation(2020M682006)the University of Science and Technology of China.
文摘Herein we report a nickel-catalyzed asymmetric two-component reductive aryl-acylation and arylcarbamoylation of aryl-iodide-tethered unactivated alkenes,which utilize ortho-pyridinyl esters and isocyanates as the electrophilic acyl sources,respectively.Under the catalysis of a nickel–pyrox complex with zinc powder as the reductant,a variety of chiral indanes,indolines,and dihydrobenzofurans bearing a quaternary stereogenic center were prepared in moderate to high efficiency and good to excellent enantioselectivities.The utility of this method is demonstrated by various simple derivatizations of the attached carbonyl group,particularly the sequential benzylic oxidation and pinacol coupling,which provide a concise entry to the benzene-fused bicyclic bridged ring framework containing three challenging tetrasubstituted stereocenters in high stereocontrol.
