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.
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 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
An unprecedented atroposelective Catellani reaction between phosphine oxide-containing aryl bromides,aryliodides,and nucleophiles for the construction of phosphine-containing biaryl atropisomers was established using ...An unprecedented atroposelective Catellani reaction between phosphine oxide-containing aryl bromides,aryliodides,and nucleophiles for the construction of phosphine-containing biaryl atropisomers was established using an enantiopure norbornene derivative as the chiral mediator.A broad range of atropisomeric biaryl-based monophosphine oxides were obtained in good efficiency with excellent enantioselectivity.展开更多
A series of structurally novel P-chiral biaryl bisphosphorus ligands L1-L5 (BABIBOPs) are developed, providing high efficiency for the first time in palladium-catalyzed asymmetric hydrogenation of β-aryl and β-alk...A series of structurally novel P-chiral biaryl bisphosphorus ligands L1-L5 (BABIBOPs) are developed, providing high efficiency for the first time in palladium-catalyzed asymmetric hydrogenation of β-aryl and β-alkyl substituted β-keto esters. With the Pd-1.3 (iPr-BABIBOP) catalyst, a series of chiral β-hydroxyl carboxylic esters are formed in excellent enantioselectivities (up to 〉 99% ee) and yields at catalyst loading as low as 0.01 mol%.展开更多
This study details Ni-catalyzed cross coupling of aryl Grignard reagents with aryl halides in toluene, a nonpolar solvent with a high boiling point. The reaction was applied for the synthesis of various biaryls in goo...This study details Ni-catalyzed cross coupling of aryl Grignard reagents with aryl halides in toluene, a nonpolar solvent with a high boiling point. The reaction was applied for the synthesis of various biaryls in good yields without the introduction of a large steric ligand. The Kumada-Tamao-Corriu(KTC) reaction in toluene was then successfully modified to proceed under neat conditions for the efficient syntheses of symmetrical biaryls, particularly in large-scale preparations. Unactivated aryl chlorides show higher reactivity than aryl bromides, particularly under neat conditions. Mechanistic investigations suggest a radical procedure for the catalytic cycle, and the origin of the radical intermediates being aryl halides.展开更多
A mild and efficient synthesis for the biaryl acids via rhodium-catalyzed cross-dehydrogenative coupling reaction has been developed. This novel protocol with sodium chlorite as an oxidant featured many advantages suc...A mild and efficient synthesis for the biaryl acids via rhodium-catalyzed cross-dehydrogenative coupling reaction has been developed. This novel protocol with sodium chlorite as an oxidant featured many advantages such as mild reaction conditions, high regioselectivity, tolerance of various functional groups, and good to excellent yields.展开更多
A strategy for Pd-catalyzed ortho-C–H silylation of biaryl aldehydes enabled by a transient auxiliary is presented. This protocol provides a broad range of ortho-silylated biaryl aldehydes in good yields. The silyl m...A strategy for Pd-catalyzed ortho-C–H silylation of biaryl aldehydes enabled by a transient auxiliary is presented. This protocol provides a broad range of ortho-silylated biaryl aldehydes in good yields. The silyl moiety can be further functionalized under mild conditions, rendering the silylated products useful building blocks. Notably, this protocol also offers an opportunity to establish a platform for expeditious synthesis of structurally diverse axially chiral biaryl aldehydes via sequential atroposelective interannular C–H functionalization/intraanular C–H silylation.展开更多
Application of the Suzuki cross-coupling reaction for efficient synthesis of diverse substituted biaryl-chromen- 4-ones using an optimized palladium(0) catalyst system is reported. The coupling of arylboronic acids ...Application of the Suzuki cross-coupling reaction for efficient synthesis of diverse substituted biaryl-chromen- 4-ones using an optimized palladium(0) catalyst system is reported. The coupling of arylboronic acids with the resin-bound bromoflavanones which were prepared by organoselenium-induced regioselective intramolecular cy- clization of bromo-2-hydroxylchalcones proceeded smoothly. Biaryl-chromen-4-ones were synthesized by subse- quent selenoxide syn-elimination in good total yields.展开更多
The stereocontrol of chiral metal clusters and nanoclusters has become a focus of interest in metal cluster chemistry due to their promising applications in asymmetric catalysis.Despite being a general chirality trans...The stereocontrol of chiral metal clusters and nanoclusters has become a focus of interest in metal cluster chemistry due to their promising applications in asymmetric catalysis.Despite being a general chirality transfer strategy,the ion-pairing process is still ambiguous in the course of bestowing chirality to metal clusters.Here we construct a biaryl-centered axially chiral gold-cluster system to study an outside-in ion-pairing chirality transfer process.Four hexanuclear gold(I)clusters,centered by two types of biaryl ligands[(2-indolyl)aniline(L^(1))and biindole(L^(2))],were synthesized via in situ cyclization reactions.In the crystalline state,the biaryl centers showed axial chirality in which the gold atoms were in an asymmetric arrangement.In solution,the chiral phosphates induced an outside-in chirality transfer by significant interactions with the periphery of the biaryl-centered gold clusters.Finally,the chiral resolution of hexa-aurated biindoliums was accomplished via an efficient outside-in chirality transfer process relying on strong aurophilic interaction and extra peripheral coordination.This study not only deepens the understanding of the outside-in ion-pairing chirality transfer process but also provides a new approach for fabricating desired chiral metal clusters by a combination of organometallic transformation and chirality transfer.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
Salicylaldehyde containing biaryls are efficiently synthesized via an unprecedented amine promoted Diels-Alderretro-Diels-Alder cascade reaction of ynals with 2-pyrones in good yields.The reaction is instrumentally me...Salicylaldehyde containing biaryls are efficiently synthesized via an unprecedented amine promoted Diels-Alderretro-Diels-Alder cascade reaction of ynals with 2-pyrones in good yields.The reaction is instrumentally metalfree,operationally simple and mild,and tolerates a diverse array of functional groups.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
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.
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
基金Financial support from National Natural Science Foundation of China(nos.21772046 and 2193103)is gratefully acknowledged.
文摘An unprecedented atroposelective Catellani reaction between phosphine oxide-containing aryl bromides,aryliodides,and nucleophiles for the construction of phosphine-containing biaryl atropisomers was established using an enantiopure norbornene derivative as the chiral mediator.A broad range of atropisomeric biaryl-based monophosphine oxides were obtained in good efficiency with excellent enantioselectivity.
基金The work is supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000), CAS (QYZDY-SSW-SLH029), the National Natural Science Foundation of China (Nos. 21432007, 21572246, 21725205) and K C. Wong Education Foundation.
文摘A series of structurally novel P-chiral biaryl bisphosphorus ligands L1-L5 (BABIBOPs) are developed, providing high efficiency for the first time in palladium-catalyzed asymmetric hydrogenation of β-aryl and β-alkyl substituted β-keto esters. With the Pd-1.3 (iPr-BABIBOP) catalyst, a series of chiral β-hydroxyl carboxylic esters are formed in excellent enantioselectivities (up to 〉 99% ee) and yields at catalyst loading as low as 0.01 mol%.
文摘This study details Ni-catalyzed cross coupling of aryl Grignard reagents with aryl halides in toluene, a nonpolar solvent with a high boiling point. The reaction was applied for the synthesis of various biaryls in good yields without the introduction of a large steric ligand. The Kumada-Tamao-Corriu(KTC) reaction in toluene was then successfully modified to proceed under neat conditions for the efficient syntheses of symmetrical biaryls, particularly in large-scale preparations. Unactivated aryl chlorides show higher reactivity than aryl bromides, particularly under neat conditions. Mechanistic investigations suggest a radical procedure for the catalytic cycle, and the origin of the radical intermediates being aryl halides.
文摘A mild and efficient synthesis for the biaryl acids via rhodium-catalyzed cross-dehydrogenative coupling reaction has been developed. This novel protocol with sodium chlorite as an oxidant featured many advantages such as mild reaction conditions, high regioselectivity, tolerance of various functional groups, and good to excellent yields.
基金supported by the National Natural Science Foundation of China (21925109, 21772170)the Outstanding Young Talents of Zhejiang Province High-level Personnel of Special Support (ZJWR0108)+1 种基金the Fundamental Research Funds for the Central Universities (2018XZZX001-02)Zhejiang Provincial Natural Science Foundation (LR17B020001)。
文摘A strategy for Pd-catalyzed ortho-C–H silylation of biaryl aldehydes enabled by a transient auxiliary is presented. This protocol provides a broad range of ortho-silylated biaryl aldehydes in good yields. The silyl moiety can be further functionalized under mild conditions, rendering the silylated products useful building blocks. Notably, this protocol also offers an opportunity to establish a platform for expeditious synthesis of structurally diverse axially chiral biaryl aldehydes via sequential atroposelective interannular C–H functionalization/intraanular C–H silylation.
文摘Application of the Suzuki cross-coupling reaction for efficient synthesis of diverse substituted biaryl-chromen- 4-ones using an optimized palladium(0) catalyst system is reported. The coupling of arylboronic acids with the resin-bound bromoflavanones which were prepared by organoselenium-induced regioselective intramolecular cy- clization of bromo-2-hydroxylchalcones proceeded smoothly. Biaryl-chromen-4-ones were synthesized by subse- quent selenoxide syn-elimination in good total yields.
基金National Natural Science Foundation of China(21772111,21821001,91956125,and 21661132006).
文摘The stereocontrol of chiral metal clusters and nanoclusters has become a focus of interest in metal cluster chemistry due to their promising applications in asymmetric catalysis.Despite being a general chirality transfer strategy,the ion-pairing process is still ambiguous in the course of bestowing chirality to metal clusters.Here we construct a biaryl-centered axially chiral gold-cluster system to study an outside-in ion-pairing chirality transfer process.Four hexanuclear gold(I)clusters,centered by two types of biaryl ligands[(2-indolyl)aniline(L^(1))and biindole(L^(2))],were synthesized via in situ cyclization reactions.In the crystalline state,the biaryl centers showed axial chirality in which the gold atoms were in an asymmetric arrangement.In solution,the chiral phosphates induced an outside-in chirality transfer by significant interactions with the periphery of the biaryl-centered gold clusters.Finally,the chiral resolution of hexa-aurated biindoliums was accomplished via an efficient outside-in chirality transfer process relying on strong aurophilic interaction and extra peripheral coordination.This study not only deepens the understanding of the outside-in ion-pairing chirality transfer process but also provides a new approach for fabricating desired chiral metal clusters by a combination of organometallic transformation and chirality transfer.
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The work was supported by the National Natural Science Foundation of China(No.21738002).
文摘Salicylaldehyde containing biaryls are efficiently synthesized via an unprecedented amine promoted Diels-Alderretro-Diels-Alder cascade reaction of ynals with 2-pyrones in good yields.The reaction is instrumentally metalfree,operationally simple and mild,and tolerates a diverse array of functional groups.
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.