A series of symmetrical biaryls was synthesized from arylmercuric chlorides and biarylmercurials in the presence of [ClRh(CO) 2] 2 in hexamethylphosphoramide(HMPA). The mechanism of the [ClRh(CO) 2] 2 catalyzed d...A series of symmetrical biaryls was synthesized from arylmercuric chlorides and biarylmercurials in the presence of [ClRh(CO) 2] 2 in hexamethylphosphoramide(HMPA). The mechanism of the [ClRh(CO) 2] 2 catalyzed dimerization of biarylmercurials was studied, and shown to be mainly intermolecular reaction.展开更多
In the case of Pd(PPh3)4 as catalyst and toluene as reaction solvent, the desired biaryls and polyaryls were synthesized in excellent yield and on a large scale.
Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proc...Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proceeded under simple,green,and mild conditions.The peptide nanofibers were used as recyclable supports in the coupling reactions.This approach is the first to use hydroxybenzotriazole as a phenylating agent.展开更多
Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium（0） complex. Thi...Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium（0） complex. This palladium complex can be easily recovered and reused many times without loss of activity.展开更多
The central-to-axial chirality conversion represents a fascinating class of chemical processes consisting of the destruction of stereogenic centers and the simultaneous installation of axial chiral elements,which prov...The central-to-axial chirality conversion represents a fascinating class of chemical processes consisting of the destruction of stereogenic centers and the simultaneous installation of axial chiral elements,which provides efficient methods for the preparation of axially chiral compounds.However,developing catalytic asymmetric approaches for constructing these central chirality precursors and the efficient central-to-axial chirality conversion remains a challenge due to the requirement of aromatization or elimination process.In this work,we have developed an unprecedented enantioselective intramolecular FriedelCrafts alkylation with unactivated-ketone carbonyls from which a chiral tertiary alcohol was generated with high efficiency and excellent enantioselectivity.In addition,the central-to-axial chirality conversion strategy has been successfully applied to the synthesis of enantioenriched biaryls via a less-explored carbocation-initiated rearrangement and aromatization under the promotion of Lewis acid.This methodology provided a straightforward and sustainable access to a broad range of biaryl-2-carboxylic acid and in excellent yields(up to 92%)and excellent central-to-axial chirality conversion(up to 99%conversion percentage).This work could be a great model for developing new methods for synthesizing axially chiral biaryls and a general protocol for the rearrangement and aromatization of carbocations for further functionalization.展开更多
Axially chiral biaryls represent the most important class of atropisomers,and they widely exist in natural products and biologically active molecules.They also constitute a unique scaffold for chiral ligands and catal...Axially chiral biaryls represent the most important class of atropisomers,and they widely exist in natural products and biologically active molecules.They also constitute a unique scaffold for chiral ligands and catalysts in organic synthesis.The development of synthetic methods to obtain such chiral compounds has received widespread attention,among which catalytically atroposelective ring-opening of configurationally labile compounds represents one of the most attractive strategies.Various substrates with strained cyclic structures,such as the renowned Bringmann's lactones,can undergo asymmetric transformation into stable atropisomers.Known advancement primarily relies on metal catalyst combined with well-designed chiral ligands,the approaches utilizing organocatalysis as a critical resolution strategy are notably scarce.In this study,we disclosed a N-heterocyclic carbene(NHC)-catalyzed asymmetric ring-opening reaction of biaryl lactams via direct atroposelective nucleophilic activation.The optimized bulky carbene catalyst ensures that the reaction can proceed under mild conditions,affording the desired product with good to excellent yields and atroposelectivity.展开更多
A domino [4+2]/retro [4+2] cycloaddition process of cyclohexadienes with arylethynes or benzyne providing access to biaryls and polycyclic aromatics has been studied theoretically using density functional theory calcu...A domino [4+2]/retro [4+2] cycloaddition process of cyclohexadienes with arylethynes or benzyne providing access to biaryls and polycyclic aromatics has been studied theoretically using density functional theory calculations. It has been found that the initial Diels-Alder (D-A) reaction acts as the rate-determining step and the consequent [4+2] cycloreversion reaction is feasible under the conditions used. Furthermore, the D-A reaction affects the regioselectivity, the origin of which is essentially derived from the good match of orbital coefficients between dienes and dienophiles as shown by using frontier molecular orbital (FMO) theory. Further investigation of the reactivity reveals that the reactions are predicted to fail to occur if an electron-donor group in the diene or an electron-acceptor group in the dienophile is lacking, as a consequence of the increased FMO energy gap. By further exploring the scope of substrates computationally, benzyne as an active dienophile was predicted to react with a variety of dienes in a cascade reaction under mild conditions with a low energy barrier, with the rate-determining step being the retro [4+2] cycloaddition.展开更多
The merging of C-H and C-C bond cleavage into one single chemical process remains a daunting challenge,especially in an asymmetric manner.Herein,a Pd(Ⅱ)-catalyzed enantioselective tandem C-H/C-C activation for the sy...The merging of C-H and C-C bond cleavage into one single chemical process remains a daunting challenge,especially in an asymmetric manner.Herein,a Pd(Ⅱ)-catalyzed enantioselective tandem C-H/C-C activation for the synthesis of axially chiral biaryls is described.Two types of simple cyclopropanes,such as vinylcyclopropanes and cyclopropanols,were used as efficient and readily available coupling partners.展开更多
Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain correspond...Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain corresponding biaryls in excellent yields. The recycling of the polymer-bound catalyst was tested without adding palladium.展开更多
In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects o...In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.展开更多
Suzuki cross-coupling reaction of phenylboronic acid with aryl halides catalyzed by cyclopalladated complexes of tertiary arylamines immobilized in ionic liquid [Bmim]^＋BF4^- was reported. The catalytic system proved...Suzuki cross-coupling reaction of phenylboronic acid with aryl halides catalyzed by cyclopalladated complexes of tertiary arylamines immobilized in ionic liquid [Bmim]^＋BF4^- was reported. The catalytic system proved to be efficient and be reused at least 3 times without significant loss of activity.展开更多
The isoindolinone and biaryl scaffolds are prevalent in natural products and drug molecules,which have showed broad and interesting biological activities.The efficient construction of such hybridized molecules and bio...The isoindolinone and biaryl scaffolds are prevalent in natural products and drug molecules,which have showed broad and interesting biological activities.The efficient construction of such hybridized molecules and biological evaluation are of great interest to medicinal chemistry community.In this communication,we report an efficient BrΦnsted acid-promoted C(sp^3)-H functionalization approach that enables the rapid construction of biologically important isoindolinone/[1,2,4]triazolo[1,5-a]pyrimidine hybrids from 5-methyl-7-(2,4,6-trimethoxyphenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,2-formylbenzoic acid and various anilines.The title compounds were generated in high to excellent yields(up to 96%)regardless of the electronic nature and steric effects of the substituents.In this reaction,an isoindolinone scaffold,one C-C single bond,and two C-N bonds were formed simultaneously with high atom economy.In this work,we have envisioned that the methyl group linked to the electron-deficient Nheterocycles could be used as a new synthetic handle for late-state diversification and may have broad applications in the field of organic and medicinal chemistry.Besides,the title compounds have exhibited promising activity against the SKP2-CKS1 interaction.展开更多
Some novel cycloaddition reactions based on benzyne and olefins have been developed.These reactions were performed in the absence of a transition metal catalyst,and they displayed good yields.These cycloaddition react...Some novel cycloaddition reactions based on benzyne and olefins have been developed.These reactions were performed in the absence of a transition metal catalyst,and they displayed good yields.These cycloaddition reactions of benzyne with olefins provide effective routes for synthesizing benzocyclobutenes,biaryl compounds and 9,10-dihydrophenanthrene derivatives.展开更多
The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene- 1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with ...The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene- 1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with elemental analyses, 1H NMR spectra and 13C NMR spectra.展开更多
The novel organometallic compounds, 3-[4'(or 2')-(4''-fluorophenyl)] phenyl-1-ferroc- enyl-2-propen-1-ones 5 were synthesized for nonlinear optical chromophores by Pd (0) catalyzed Suzuki cross-coupl...The novel organometallic compounds, 3-[4'(or 2')-(4''-fluorophenyl)] phenyl-1-ferroc- enyl-2-propen-1-ones 5 were synthesized for nonlinear optical chromophores by Pd (0) catalyzed Suzuki cross-coupling reaction. Their structures were established with elemental analysis, MS, IR and H NMR spectroscopies. 1展开更多
Nation-Teflon bimembrane was used as an efficient support for the preparation and application of heterogeneous palladium catalysts. The supported palladium catalysts exhibit high activity and stability in the Suzuki c...Nation-Teflon bimembrane was used as an efficient support for the preparation and application of heterogeneous palladium catalysts. The supported palladium catalysts exhibit high activity and stability in the Suzuki cross-coupling of aryl bromides with arylboronic acids to afford the corresponding biaryls in good to excellent yields, and can be readily recovered and reused several times without significant loss of activity.展开更多
Transition metal-catalyzed asymmetric reductive coupling of two electrophiles has emerged as a powerful tool for carbon–carbon bond formation;however,the enantioselective reductive cross-coupling of two aryl halides ...Transition metal-catalyzed asymmetric reductive coupling of two electrophiles has emerged as a powerful tool for carbon–carbon bond formation;however,the enantioselective reductive cross-coupling of two aryl halides has not been developed and remains a challenge.Herein,we demonstrated the enantioselective reductive cross-coupling of two aryl halides by combining cobalt catalysis with electrochemistry to afford axially chiral biaryls with good chemoselectivities(cross-coupling:homo-coupling>20:1)and enantioselectivities(up to 94%ee).This strategy could be extended to the asymmetric crosscouplings of aryl and vinyl halides to provide axially chiral non-C2-symmetric compounds with excellent chemoselectivities(cross-coupling:homo-coupling>20:1)and enantioselectivities(up to 99%ee).Density functional theory calculations and control experiments suggested that high chemo-and enantioselectivities could be realized by selective cathodic reduction of an aryl cobalt(III)species from the first oxidative addition owing to the different redox potentials.展开更多
Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in orga...Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in organic synthesis,and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction.Here,we report a photocatalytic cascade radical addition of biaryl ynones,for the divergent synthesis of privileged carbon cycles.Additionally,further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.展开更多
The first total synthesis of neopetromin,featuring the highly strained Tyr C-6-to-Trp N-1’linkage,is hereby reported.This modular synthetic strategy,employing C—H arylation and Larock macrocyclization,offers a novel...The first total synthesis of neopetromin,featuring the highly strained Tyr C-6-to-Trp N-1’linkage,is hereby reported.This modular synthetic strategy,employing C—H arylation and Larock macrocyclization,offers a novel approach to the synthesis of various RiPPs natural product families.展开更多
基金Supported by the Scientific Research Foundation for Returned Overseas Chinese Scholarsof Educational Ministry ofChina
文摘A series of symmetrical biaryls was synthesized from arylmercuric chlorides and biarylmercurials in the presence of [ClRh(CO) 2] 2 in hexamethylphosphoramide(HMPA). The mechanism of the [ClRh(CO) 2] 2 catalyzed dimerization of biarylmercurials was studied, and shown to be mainly intermolecular reaction.
基金Support from the University of Science and Technology of China the National Natural Science Foundation of China are gratefully acknowledged (NO. 50073021).
文摘In the case of Pd(PPh3)4 as catalyst and toluene as reaction solvent, the desired biaryls and polyaryls were synthesized in excellent yield and on a large scale.
基金the Research Facility of Ilam University,Ilam,Iran,for financial support of this research project
文摘Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proceeded under simple,green,and mild conditions.The peptide nanofibers were used as recyclable supports in the coupling reactions.This approach is the first to use hydroxybenzotriazole as a phenylating agent.
基金National Natural Science Foundation of China （Project 20462002） Natural Science Foundation of Jiangxi Province （Project 0420015） for financial support.
文摘Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium（0） complex. This palladium complex can be easily recovered and reused many times without loss of activity.
基金supported by the National Natural Science Foundation of China(22022704,21977097,22271291),Chinese Academy of Sciences。
文摘The central-to-axial chirality conversion represents a fascinating class of chemical processes consisting of the destruction of stereogenic centers and the simultaneous installation of axial chiral elements,which provides efficient methods for the preparation of axially chiral compounds.However,developing catalytic asymmetric approaches for constructing these central chirality precursors and the efficient central-to-axial chirality conversion remains a challenge due to the requirement of aromatization or elimination process.In this work,we have developed an unprecedented enantioselective intramolecular FriedelCrafts alkylation with unactivated-ketone carbonyls from which a chiral tertiary alcohol was generated with high efficiency and excellent enantioselectivity.In addition,the central-to-axial chirality conversion strategy has been successfully applied to the synthesis of enantioenriched biaryls via a less-explored carbocation-initiated rearrangement and aromatization under the promotion of Lewis acid.This methodology provided a straightforward and sustainable access to a broad range of biaryl-2-carboxylic acid and in excellent yields(up to 92%)and excellent central-to-axial chirality conversion(up to 99%conversion percentage).This work could be a great model for developing new methods for synthesizing axially chiral biaryls and a general protocol for the rearrangement and aromatization of carbocations for further functionalization.
基金the Natural Science Foundation of Jiangsu Province(BK20221309)the National Natural Science Foundation of China(21602105).
文摘Axially chiral biaryls represent the most important class of atropisomers,and they widely exist in natural products and biologically active molecules.They also constitute a unique scaffold for chiral ligands and catalysts in organic synthesis.The development of synthetic methods to obtain such chiral compounds has received widespread attention,among which catalytically atroposelective ring-opening of configurationally labile compounds represents one of the most attractive strategies.Various substrates with strained cyclic structures,such as the renowned Bringmann's lactones,can undergo asymmetric transformation into stable atropisomers.Known advancement primarily relies on metal catalyst combined with well-designed chiral ligands,the approaches utilizing organocatalysis as a critical resolution strategy are notably scarce.In this study,we disclosed a N-heterocyclic carbene(NHC)-catalyzed asymmetric ring-opening reaction of biaryl lactams via direct atroposelective nucleophilic activation.The optimized bulky carbene catalyst ensures that the reaction can proceed under mild conditions,affording the desired product with good to excellent yields and atroposelectivity.
基金supported by the National Natural Science Foundation of China (21172017, 20972013 and 20772005)the specialized Research Fund for the Doctoral Program of Higher Education, Ministry of Education of China (20110010110011)"CHEMCLOUD COMPUTING " of Beijing University of Chemical Technology
文摘A domino [4+2]/retro [4+2] cycloaddition process of cyclohexadienes with arylethynes or benzyne providing access to biaryls and polycyclic aromatics has been studied theoretically using density functional theory calculations. It has been found that the initial Diels-Alder (D-A) reaction acts as the rate-determining step and the consequent [4+2] cycloreversion reaction is feasible under the conditions used. Furthermore, the D-A reaction affects the regioselectivity, the origin of which is essentially derived from the good match of orbital coefficients between dienes and dienophiles as shown by using frontier molecular orbital (FMO) theory. Further investigation of the reactivity reveals that the reactions are predicted to fail to occur if an electron-donor group in the diene or an electron-acceptor group in the dienophile is lacking, as a consequence of the increased FMO energy gap. By further exploring the scope of substrates computationally, benzyne as an active dienophile was predicted to react with a variety of dienes in a cascade reaction under mild conditions with a low energy barrier, with the rate-determining step being the retro [4+2] cycloaddition.
基金The authors gratefully acknowledge financial support from the NSFC(nos.21772170 and 21925109 for B.-F.S.and no.21901228 for G.L.)Outstanding Young Talents of Zhejiang Province High-level Personnel of Special Support(no.ZJWR0108 for B.-F.S.).
文摘The merging of C-H and C-C bond cleavage into one single chemical process remains a daunting challenge,especially in an asymmetric manner.Herein,a Pd(Ⅱ)-catalyzed enantioselective tandem C-H/C-C activation for the synthesis of axially chiral biaryls is described.Two types of simple cyclopropanes,such as vinylcyclopropanes and cyclopropanols,were used as efficient and readily available coupling partners.
基金This work was financially supported by the Knowledge Innovation Program of the Chinese Academy of Sciences(DICP R200309)the National Basic Research Program of China(2003CB61615803)the National Natural Science Foundation of China(No.20473089).
文摘Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain corresponding biaryls in excellent yields. The recycling of the polymer-bound catalyst was tested without adding palladium.
基金the NSFC(No.20272037),the Doctor's Foundation of Education Ministry of China(No.20030610022)Foundation of Xihua University(No.R0723315) and(No.07ZA109) for the financial support of this work.
文摘In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.
基金Project supported by the National Natural Science Foundation of China(No.20172016)Shanghai Science&Technology Council(04JC14032).
文摘Suzuki cross-coupling reaction of phenylboronic acid with aryl halides catalyzed by cyclopalladated complexes of tertiary arylamines immobilized in ionic liquid [Bmim]^＋BF4^- was reported. The catalytic system proved to be efficient and be reused at least 3 times without significant loss of activity.
基金supported by the National Natural Science Foundation of China(Nos.81773562 and 81703326)China Postdoctoral Science Foundation(Nos.2018M630840 and 2019T120641)Scientific Program of Henan Province(No.182102310123)。
文摘The isoindolinone and biaryl scaffolds are prevalent in natural products and drug molecules,which have showed broad and interesting biological activities.The efficient construction of such hybridized molecules and biological evaluation are of great interest to medicinal chemistry community.In this communication,we report an efficient BrΦnsted acid-promoted C(sp^3)-H functionalization approach that enables the rapid construction of biologically important isoindolinone/[1,2,4]triazolo[1,5-a]pyrimidine hybrids from 5-methyl-7-(2,4,6-trimethoxyphenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,2-formylbenzoic acid and various anilines.The title compounds were generated in high to excellent yields(up to 96%)regardless of the electronic nature and steric effects of the substituents.In this reaction,an isoindolinone scaffold,one C-C single bond,and two C-N bonds were formed simultaneously with high atom economy.In this work,we have envisioned that the methyl group linked to the electron-deficient Nheterocycles could be used as a new synthetic handle for late-state diversification and may have broad applications in the field of organic and medicinal chemistry.Besides,the title compounds have exhibited promising activity against the SKP2-CKS1 interaction.
基金financial support from the National Natural Science Foundation of China(Nos.20931006,21072070, 21072071,21272088)the Program for Academic Leader in Wuhan Municipality(No.201271130441)
文摘Some novel cycloaddition reactions based on benzyne and olefins have been developed.These reactions were performed in the absence of a transition metal catalyst,and they displayed good yields.These cycloaddition reactions of benzyne with olefins provide effective routes for synthesizing benzocyclobutenes,biaryl compounds and 9,10-dihydrophenanthrene derivatives.
文摘The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene- 1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with elemental analyses, 1H NMR spectra and 13C NMR spectra.
文摘The novel organometallic compounds, 3-[4'(or 2')-(4''-fluorophenyl)] phenyl-1-ferroc- enyl-2-propen-1-ones 5 were synthesized for nonlinear optical chromophores by Pd (0) catalyzed Suzuki cross-coupling reaction. Their structures were established with elemental analysis, MS, IR and H NMR spectroscopies. 1
文摘Nation-Teflon bimembrane was used as an efficient support for the preparation and application of heterogeneous palladium catalysts. The supported palladium catalysts exhibit high activity and stability in the Suzuki cross-coupling of aryl bromides with arylboronic acids to afford the corresponding biaryls in good to excellent yields, and can be readily recovered and reused several times without significant loss of activity.
基金supported by the National Key R&D Program of China(grant no.2021YFA1500100)the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB0610000)+1 种基金the NSF of China(grant nos.21821002 and 22361142834)Natural Science Foundation of Ningbo(grant no.2023J035).
文摘Transition metal-catalyzed asymmetric reductive coupling of two electrophiles has emerged as a powerful tool for carbon–carbon bond formation;however,the enantioselective reductive cross-coupling of two aryl halides has not been developed and remains a challenge.Herein,we demonstrated the enantioselective reductive cross-coupling of two aryl halides by combining cobalt catalysis with electrochemistry to afford axially chiral biaryls with good chemoselectivities(cross-coupling:homo-coupling>20:1)and enantioselectivities(up to 94%ee).This strategy could be extended to the asymmetric crosscouplings of aryl and vinyl halides to provide axially chiral non-C2-symmetric compounds with excellent chemoselectivities(cross-coupling:homo-coupling>20:1)and enantioselectivities(up to 99%ee).Density functional theory calculations and control experiments suggested that high chemo-and enantioselectivities could be realized by selective cathodic reduction of an aryl cobalt(III)species from the first oxidative addition owing to the different redox potentials.
基金the Natural Science Foundation of Zhejiang Province(LY22B020001)the Zhejiang Public Welfare Public Research Program(LGC22B010001)the National Natural Science Foundation of China(32201238)is greatly acknowledged.
文摘Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in organic synthesis,and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction.Here,we report a photocatalytic cascade radical addition of biaryl ynones,for the divergent synthesis of privileged carbon cycles.Additionally,further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.
基金Financial support for this work was provided by a grant from the RGC of the Hong Kong SAR,China(ECS,HKUST 26302024)start-up funds from HKUST(Project No.R9820)to H.N+2 种基金This work was partly supported by JSPS KAKENHI Grant Number JP23H03810,JST-ERATO(JPMJER1903)the Institute for Chemical Reaction Design and Discovery(ICReDD),which was established by the World Premier International Research Initiative(WPI),MEXT,Japan(Y.N.)The computation was partly performed using Research Center for Computational Science,Okazaki,Japan(Project:23-IMS-C119,Y.N.).
文摘The first total synthesis of neopetromin,featuring the highly strained Tyr C-6-to-Trp N-1’linkage,is hereby reported.This modular synthetic strategy,employing C—H arylation and Larock macrocyclization,offers a novel approach to the synthesis of various RiPPs natural product families.
