A visible-light-induced spirocyclizative hydroarylation via reductive dearomatization of a series of non activated arenes including 2-phenyl indoles and naphthalene derivatives under mild conditions is de scribed.An i...A visible-light-induced spirocyclizative hydroarylation via reductive dearomatization of a series of non activated arenes including 2-phenyl indoles and naphthalene derivatives under mild conditions is de scribed.An intriguing chemoselective dearomative hydroarylation of 2-phenyl indoles is presented.Th dearomative hydroarylation protocol rapidly delivers valuable spirocycles with carbon-carbon doub bonds from readily accessible aromatic precursors in a single step.展开更多
The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low(400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multigram scale. It ...The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low(400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multigram scale. It is suitable for the synthesis of alkenes labeled with deuterium, and for the late-stage modification of bioactive molecules.展开更多
Herein,we report an intramolecular 6-endo-dig cyclization of N-ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation.By using this protocol,a variety of pla...Herein,we report an intramolecular 6-endo-dig cyclization of N-ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation.By using this protocol,a variety of planar chiral ferrocenopyridin-2(1H)-ones were obtained in good yields and excellent enantioselectivities(up to 96%ee).展开更多
The use of simple and easily available feedstock to quickly and efficiently obtain compounds with complex molecular structures through the transition-metal-catalyzed construction of C(sp3)–C bonds has important signi...The use of simple and easily available feedstock to quickly and efficiently obtain compounds with complex molecular structures through the transition-metal-catalyzed construction of C(sp3)–C bonds has important significance.As traditional C(sp3)–C coupling reagents,alkylmetallic reagents often have limitations such as air and moisture sensitivity and difficulties in storage.Nickel-catalyzed reductive olefin hydrocarbonation reactions use alkenes to replace organometallic reagents,reduce the synthesis steps,improve the functional group compatibility,and expand the substrate scope.This minireview discusses important progress in the hydroalkylation and hydroarylation of electronically unbiased alkenes in recent years and describes the key mechanism and applications.展开更多
A highly efficient kinetic resolution of racemic 2-substituted 1,2-dihydroquinolines via Rh-catalyzed asymmetric hydroarylation has been described for the first time.A variety of arylboronic acids coupled with 2-subst...A highly efficient kinetic resolution of racemic 2-substituted 1,2-dihydroquinolines via Rh-catalyzed asymmetric hydroarylation has been described for the first time.A variety of arylboronic acids coupled with 2-substituted 1,2-dihydroquinolines under mild reaction condition.The transformations into the enantio-enriched 2,3-diaryl-tetrahydroquinolines as well as the recovered chiral 2-aryl-dihydroquinolines were obtained with high yields and excellent enantioselectivities(86%-99% ee,s factor up to 1057).展开更多
We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro amino phosphine ligands.The reaction serves as an efficient,st...We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro amino phosphine ligands.The reaction serves as an efficient,straightf orward,and mild method for the preparation of enantio enriched 1,1-diarylalkanes,which are important building blocks for the synthesis of many biologically active molecules.This redox neutral reaction uses only catalytic amounts of the reagents and is,therefore,atom economical and environmentally benign.展开更多
The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asym...The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives.展开更多
A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light cata...A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C?C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.展开更多
Compound 1, N-methyl-N-（（2-（p-tolyl）quinolin-4-yl）methyl）aniline （C24H22N2）, as a potential drug for the treatment of acid-related diseases has been synthesized via palladium- catalyzed intramolecular hydroary...Compound 1, N-methyl-N-（（2-（p-tolyl）quinolin-4-yl）methyl）aniline （C24H22N2）, as a potential drug for the treatment of acid-related diseases has been synthesized via palladium- catalyzed intramolecular hydroarylation. The compound was characterized by MS and NMR spectra. Meanwhile, the crystal of I was obtained and determined by X-ray single-crystal diffrac- tion. Crystal data： triclinic system, space group P1, a = 5.548（5）, b = 11.545（10）, c = 14.546（12）A, a = 90.427（15）, β = 90.727（14）, γ = 101.099（16）°, V= 914.1（13） A3, Z = 2, F（000） = 360, Dc = 1.230 g/cm3,μ = 0.072 mm-1, R = 0.0564 and wR = 0.1616 for 9768 independent reflections （Rint = 0.0447） and 3003 observed ones （I 〉 2σ（I））.展开更多
Herein,we report the migratory hydroarylation of unactivated alkenes with aryl iodides using native and weakly coordinating amide directors under mild conditions.Synergistic coordination of the monodentate directing g...Herein,we report the migratory hydroarylation of unactivated alkenes with aryl iodides using native and weakly coordinating amide directors under mild conditions.Synergistic coordination of the monodentate directing group and the ligand enable the highly regioselective migratory hydroarylation via a chain walking process to form the thermodynamically stable five-membered nickelacyle intermediate.The protocol provides a variety of valuableα-aryl-substituted alkylamine products,and exhibited good functional group tolerance.The modification of bioactive compounds such as fenofibrate and indomethacin further highlights the synthetic value of this protocol.展开更多
A novel series of naphtho-ferrocene derivatives were synthesized in high yields by an efficient gold-catalyzed intramolecular 6-endo-dig cyclization strategy. The salient features of this reaction include easy operati...A novel series of naphtho-ferrocene derivatives were synthesized in high yields by an efficient gold-catalyzed intramolecular 6-endo-dig cyclization strategy. The salient features of this reaction include easy operation, broad substrate scope, high yields, mild conditions and it works well in wet solvent under air at room temperature.展开更多
Chiral dialkyl carbinols and their derivatives are significant synthetic building blocks in organic chemistry and related fields.The development of convenient and efficient methods to access these compounds has long b...Chiral dialkyl carbinols and their derivatives are significant synthetic building blocks in organic chemistry and related fields.The development of convenient and efficient methods to access these compounds has long been an important endeavor.Herein,we report a NiH-catalyzed reductive hydroalkylation and hydroarylation of enol esters and ethers.α-Oxoalkyl organonickel species were generated in situ in a catalytic mode and then participated in cross-coupling with alkyl or aryl halides.This approach enabled C(sp^(3))–C(sp^(3))and C(sp^(3))–C(sp^(2))bond formation under mild reductive conditions with simple operations,thereby boosting a broad substrate scope and good functional compatibility.Esters of enantioenriched dialkyl carbinols were accessed in a catalytic asymmetric version.Mechanistic studies demonstrated that this reaction proceeded through a syn-addition of Ni–H intermediate to an enol ester with high regio-and enantioselectivity.展开更多
Comprehensive Summary The direct use of non-prefunctionalized arene and alkane as the starting materials to construct Caryl−Calkyl bond is an unfulfilled target and approaches to this challenge rarely surface in metho...Comprehensive Summary The direct use of non-prefunctionalized arene and alkane as the starting materials to construct Caryl−Calkyl bond is an unfulfilled target and approaches to this challenge rarely surface in methodology studies.Current methods for thermocatalytic arene-alkane couplings(AAC)occur with specific substrates and/or inconvenient reagents.Herein,we report a one-pot relay bicatalysis system for AAC involving(pincer)Ir-catalyzed alkane transfer dehydrogenation and Fe(OTf)3-catalyzed olefin hydroarylation.This system exhibits broad scope and is particularly effective for alkylation of arenes with arylalkanes to form 1,1-diarylalkanes with high chemo-and regioselectivity,making it potentially useful for late-stage alkylation of complex molecules.Experimental mechanistic data provide a view into the factors controlling the regioselectivity.Finally,the strategy of dehydrogenation-enabled arene-alkane couplings has been successfully extended to a tandem catalysis by using a heterogeneous olefin hydroarylation catalyst.展开更多
Heterogeneous asymmetric catalysis is an important strategy for the industrial production of chiral compounds.Herein,we reported a polymer-bound Xu-Phos-derived palladium catalyst that shows good performance in hetero...Heterogeneous asymmetric catalysis is an important strategy for the industrial production of chiral compounds.Herein,we reported a polymer-bound Xu-Phos-derived palladium catalyst that shows good performance in heterogeneous asymmetric reductive Heck reaction of allyl aryl ethers.This heterogeneous catalyst was easily prepared by efficient immobilization of the sulfonamide phosphine ligand(Xu-Phos)in the cross-linked polystyrene via copolymerization,and exhibits similar catalytic activity and enantioselectivity to that of the homogeneous catalyst.Moreover,the heterogeneous catalyst system is proved to be easily recovered and reused several times without losing catalytic activity obviously.展开更多
基金the financial supports from the National Natural Science Foundation of China(Nos.22022111,21871257,21801240)the Natural Science Foundation of Fujian Province(No.2020J02008)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)。
文摘A visible-light-induced spirocyclizative hydroarylation via reductive dearomatization of a series of non activated arenes including 2-phenyl indoles and naphthalene derivatives under mild conditions is de scribed.An intriguing chemoselective dearomative hydroarylation of 2-phenyl indoles is presented.Th dearomative hydroarylation protocol rapidly delivers valuable spirocycles with carbon-carbon doub bonds from readily accessible aromatic precursors in a single step.
基金financial support from the National Natural Science Foundation of China (No. 21472033)the National Key R&D Program of China (No. 2018YFB1501604)the Fundamental Research Funds for the Central Universities (No. PA2020GDKC0021)。
文摘The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low(400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multigram scale. It is suitable for the synthesis of alkenes labeled with deuterium, and for the late-stage modification of bioactive molecules.
基金support from the National Natural Science Foundation of China(No.21572126)Natural Science Foundation of Henan(No.232300421234)+2 种基金Key Scientific and Technological Project of Henan Province(No.222102310372)Leading Talents in Scientific and Technological Innovation in Shangqiu(No.SQRC202212004)Shangqiu Normal University(Program of Ecological Environmental Protection in the Area of Old Course of Yellow River).
文摘Herein,we report an intramolecular 6-endo-dig cyclization of N-ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation.By using this protocol,a variety of planar chiral ferrocenopyridin-2(1H)-ones were obtained in good yields and excellent enantioselectivities(up to 96%ee).
基金This work was supported by the National Natural Science Foundation of China(21732006,21702200,51821006,51961135104)and the Fundamental Research Funds for the Central Universities.
文摘The use of simple and easily available feedstock to quickly and efficiently obtain compounds with complex molecular structures through the transition-metal-catalyzed construction of C(sp3)–C bonds has important significance.As traditional C(sp3)–C coupling reagents,alkylmetallic reagents often have limitations such as air and moisture sensitivity and difficulties in storage.Nickel-catalyzed reductive olefin hydrocarbonation reactions use alkenes to replace organometallic reagents,reduce the synthesis steps,improve the functional group compatibility,and expand the substrate scope.This minireview discusses important progress in the hydroalkylation and hydroarylation of electronically unbiased alkenes in recent years and describes the key mechanism and applications.
基金the Shenzhen Overseas High-level Talents Innovation Plan of Technical Innovation Project(No.KQJSCX20180319114439973)for financial support.
文摘A highly efficient kinetic resolution of racemic 2-substituted 1,2-dihydroquinolines via Rh-catalyzed asymmetric hydroarylation has been described for the first time.A variety of arylboronic acids coupled with 2-substituted 1,2-dihydroquinolines under mild reaction condition.The transformations into the enantio-enriched 2,3-diaryl-tetrahydroquinolines as well as the recovered chiral 2-aryl-dihydroquinolines were obtained with high yields and excellent enantioselectivities(86%-99% ee,s factor up to 1057).
基金The authors thank the National Natural Science Founda-tion of China(Grant#s.21790332 and 21532003)the“111”project(Grant#B06005)of the Ministry of Educa-tion of China for their financial support.
文摘We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro amino phosphine ligands.The reaction serves as an efficient,straightf orward,and mild method for the preparation of enantio enriched 1,1-diarylalkanes,which are important building blocks for the synthesis of many biologically active molecules.This redox neutral reaction uses only catalytic amounts of the reagents and is,therefore,atom economical and environmentally benign.
基金the National Natural Science Foundation of China(nos.21790330 and 91956000)and the“111”Project(no.B06005)of the Ministry of Education of China for financial support.
文摘The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives.
基金supported by the National Natural Science Foundation of China(2140204621172060+1 种基金21472039)the Fundamental Research Funds for the Central Universities
文摘A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C?C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.
基金Supported by the National Natural Science Foundation of China (Nos. 21102084, 21272136 and 31070313)Scientific and Technological Research Project of Hubei Provincial Department of Education (Q20111210)Science Foundation of China Three Gorges University (No. KJ2010B001)
文摘Compound 1, N-methyl-N-（（2-（p-tolyl）quinolin-4-yl）methyl）aniline （C24H22N2）, as a potential drug for the treatment of acid-related diseases has been synthesized via palladium- catalyzed intramolecular hydroarylation. The compound was characterized by MS and NMR spectra. Meanwhile, the crystal of I was obtained and determined by X-ray single-crystal diffrac- tion. Crystal data： triclinic system, space group P1, a = 5.548（5）, b = 11.545（10）, c = 14.546（12）A, a = 90.427（15）, β = 90.727（14）, γ = 101.099（16）°, V= 914.1（13） A3, Z = 2, F（000） = 360, Dc = 1.230 g/cm3,μ = 0.072 mm-1, R = 0.0564 and wR = 0.1616 for 9768 independent reflections （Rint = 0.0447） and 3003 observed ones （I 〉 2σ（I））.
基金supported by the National Natural Science Foundation of China(Nos.21901185 and 22301216)funds provided by Tianjin Normal University。
文摘Herein,we report the migratory hydroarylation of unactivated alkenes with aryl iodides using native and weakly coordinating amide directors under mild conditions.Synergistic coordination of the monodentate directing group and the ligand enable the highly regioselective migratory hydroarylation via a chain walking process to form the thermodynamically stable five-membered nickelacyle intermediate.The protocol provides a variety of valuableα-aryl-substituted alkylamine products,and exhibited good functional group tolerance.The modification of bioactive compounds such as fenofibrate and indomethacin further highlights the synthetic value of this protocol.
基金We are grateful to the Shanghai Sailing Program （No. 16YF 1402800）, the 973 programs （No. 2015CB856600）, National Natural Science Foundation of China （No. 21425205）, and Shanghai Eastern Scholar Program for financial supports.
文摘A novel series of naphtho-ferrocene derivatives were synthesized in high yields by an efficient gold-catalyzed intramolecular 6-endo-dig cyclization strategy. The salient features of this reaction include easy operation, broad substrate scope, high yields, mild conditions and it works well in wet solvent under air at room temperature.
基金the National Natural Science Foundation of China(grant nos.21732006,51821006,21927814,and 51961135104)the Strategic Priority Research Program of CAS(grant nos.XDB20000000 and XDB37040000)+1 种基金the USTC Research Funds of the Double First-Class Initiative(grant no.YD3530002002)the Users with Excellence Program of Hefei Science Center CAS(grant nos.2019HSCUE017 and 2019HSC-UE005).
文摘Chiral dialkyl carbinols and their derivatives are significant synthetic building blocks in organic chemistry and related fields.The development of convenient and efficient methods to access these compounds has long been an important endeavor.Herein,we report a NiH-catalyzed reductive hydroalkylation and hydroarylation of enol esters and ethers.α-Oxoalkyl organonickel species were generated in situ in a catalytic mode and then participated in cross-coupling with alkyl or aryl halides.This approach enabled C(sp^(3))–C(sp^(3))and C(sp^(3))–C(sp^(2))bond formation under mild reductive conditions with simple operations,thereby boosting a broad substrate scope and good functional compatibility.Esters of enantioenriched dialkyl carbinols were accessed in a catalytic asymmetric version.Mechanistic studies demonstrated that this reaction proceeded through a syn-addition of Ni–H intermediate to an enol ester with high regio-and enantioselectivity.
基金the National Key R&D Program of China(2021YFA1501700)the National Natural Science Foundation of China(21825109,21821002,22072178,22293013).
文摘Comprehensive Summary The direct use of non-prefunctionalized arene and alkane as the starting materials to construct Caryl−Calkyl bond is an unfulfilled target and approaches to this challenge rarely surface in methodology studies.Current methods for thermocatalytic arene-alkane couplings(AAC)occur with specific substrates and/or inconvenient reagents.Herein,we report a one-pot relay bicatalysis system for AAC involving(pincer)Ir-catalyzed alkane transfer dehydrogenation and Fe(OTf)3-catalyzed olefin hydroarylation.This system exhibits broad scope and is particularly effective for alkylation of arenes with arylalkanes to form 1,1-diarylalkanes with high chemo-and regioselectivity,making it potentially useful for late-stage alkylation of complex molecules.Experimental mechanistic data provide a view into the factors controlling the regioselectivity.Finally,the strategy of dehydrogenation-enabled arene-alkane couplings has been successfully extended to a tandem catalysis by using a heterogeneous olefin hydroarylation catalyst.
基金the National Key R&D Program of China(No.2021YFF0701600)NSFC(No.22031004)+2 种基金the Shanghai Municipal Education Commission(No.20212308)China Postdoctoral Science Foundation(No.2022M713667)STCSM(No.23ZR1445600).
文摘Heterogeneous asymmetric catalysis is an important strategy for the industrial production of chiral compounds.Herein,we reported a polymer-bound Xu-Phos-derived palladium catalyst that shows good performance in heterogeneous asymmetric reductive Heck reaction of allyl aryl ethers.This heterogeneous catalyst was easily prepared by efficient immobilization of the sulfonamide phosphine ligand(Xu-Phos)in the cross-linked polystyrene via copolymerization,and exhibits similar catalytic activity and enantioselectivity to that of the homogeneous catalyst.Moreover,the heterogeneous catalyst system is proved to be easily recovered and reused several times without losing catalytic activity obviously.
