A nickel-catalyzed C(sp^(2))–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the ...A nickel-catalyzed C(sp^(2))–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the reaction step and atom economy. It has been investigated that the 2,4,6-trimethylpyridine ligand was critical to achieve the optimized reactivity. This protocol provides a straightforward route for synthesizing the alkynylated free benzylamines, featuring good substrate compatibility and monoselectivity.展开更多
Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp...Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp)-C(sp^(3))and C(sp)-C(sp^(2))bonds.This presented reaction has a broad substrate scope,enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl(pseudo)halides.This presented reaction is conducted under mild conditions,tolerating many functional groups,thus suitable for the modification and synthesis of biologically active molecules.展开更多
Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of pheny...Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring.Herein,with the assistance of a practical biaryl indolyl directing template,palladium-catalyzed remote sp^(2)C-H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity.Moreover,remote meta-selective C-H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst.These meta-C-H functionalized products proved to be the superior synthetic precursors,which are difficult to access using the conventional strategy.展开更多
Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct yn...Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.展开更多
Current synthesis of α-substituted 3,6-dihydro-2H-pyrans dominantly relies on functional group transformation. Herein, a direct and practical oxidative C -H alkynylation and alkenylation of 3,6-dihydro-2H-pyran skele...Current synthesis of α-substituted 3,6-dihydro-2H-pyrans dominantly relies on functional group transformation. Herein, a direct and practical oxidative C -H alkynylation and alkenylation of 3,6-dihydro-2H-pyran skeletons with a range of potassium trifluoroborates is developed. The metal-free process is well tolerated with a wide variety of 3,6-dihydro-2H-pyrans, rapidly providing a library of 2,4-disubstituted 3,6-dihydro-2H-pyrans with diverse patterns of α-functionalities for further diversification and bioactive small molecule identification.展开更多
Sciff bases 1 and 2, .which were derived from chiral aminoalcohols, were used as figands in Ti-catalyzed asymmetric alkynylation of aldehydes. Good enantioselectivities （up to 88% ee） and high chemical yields （80-...Sciff bases 1 and 2, .which were derived from chiral aminoalcohols, were used as figands in Ti-catalyzed asymmetric alkynylation of aldehydes. Good enantioselectivities （up to 88% ee） and high chemical yields （80-90%） were obtained.展开更多
A new,selective Ru(Ⅱ)-catalyzed alkynylation reaction of isoquinolones,quinazolones and phthalazinones with readily available bromoalkynes has been developed.This reaction enables the selective construction of a new ...A new,selective Ru(Ⅱ)-catalyzed alkynylation reaction of isoquinolones,quinazolones and phthalazinones with readily available bromoalkynes has been developed.This reaction enables the selective construction of a new C(sp^(2))-C(sp)bond through C-H activation and C-Br functionalization,and offers an effective and selective route to synthesizing highly valuable alkynylated isoquinolone,quinazolone and phthalazinonederivatives with a wide substrate scope and highselectivity.展开更多
A green efficient photoredox-catalyzed decarboxylative alkynylation of carboxylic acids with alkynyl bromides has been developed.This broadly applicable protocol is presented whereinα-amino,aliphatic andα-oxy acids ...A green efficient photoredox-catalyzed decarboxylative alkynylation of carboxylic acids with alkynyl bromides has been developed.This broadly applicable protocol is presented whereinα-amino,aliphatic andα-oxy acids are converted into useful alkynylation products.The commercially-available organic photocatalyst 4CzIPN is used as the photocatalyst,organic base DBU is utilized as the base,and DMSO serves as solvent.This strategy features mild conditions,is metal-free,and is environmentally friendly.The batch and continuous-flow protocols described were applied to obtain a broader substrate scope of functionalization(more than 50 examples).Furthermore,we demonstrate that the use of microflow technology enhanced and intensified the reaction process,achieving significantly reduced reaction times(i.e.,10 min of residence time).展开更多
Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(...Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(sp^(3))-F bonds functionalization have been greatly developed,catalytic cross-coupling of trifluoromethylarenes with C-H of terminal alkynes remains a challenge.Here,we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis.Tridentate anionic ligand is pivotal to realize this C-H sp-sp^(3) cross-coupling.Moreover,this unique catalytic system is also suitable for cross-coupling of C(sp^(3))-F bonds with azoles C(sp^(2))-H bonds.A series of trifluoromethylarenes,terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products.Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.展开更多
The highly stereoselective synthesis of diverse medicinally valuable alkynyl C-glycosides under mild and green reaction conditions remains a great challenge.Herein,we wish to report a visible-light induced photocataly...The highly stereoselective synthesis of diverse medicinally valuable alkynyl C-glycosides under mild and green reaction conditions remains a great challenge.Herein,we wish to report a visible-light induced photocatalytic decarboxylative alkynylation approach.By utilizing an iridium photocatalyst in the presence of visible light,glycosyl radicals are in-situ generated via the decarboxylation of anomeric acids and efficiently coupled with a variety of ethynylbenziodoxolones(EBXs),which allows the facile synthesis of a variety of alkynyl C-glycosides in moderate to high yields and with excellent diastereoselectivity.展开更多
Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords ...Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords unprecedented C,B-substituted carborane-fused-pyridone derivatives, whereas the use of terminal alkynes leads to B–H/C(sp)–H dehydrocoupling products. The isolation and structural identification of a notably stable Cu(Ⅰ) intermediate shed light on the reaction mechanism, which is proposed to involve a Cu(Ⅲ) intermediate.展开更多
Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylate...Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes.This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups.Mechanistically,the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation.The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.展开更多
Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for the construction of chiral alkynes.The asymmetric C(sp^(3))–C(sp)cross...Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for the construction of chiral alkynes.The asymmetric C(sp^(3))–C(sp)cross-coupling provides a significant complementary strategy through radical-initiated process.However,the stereocontrol of highly reactive and unstable radical intermediate has been a challenge for decades.To address this problem,a variety of chiral ligands are developed for initiating the reaction and achieving enantiocontrol of alkyl radicals.This review summarizes recent developments in copper-catalyzed enantioselective alkynylation of prochiral alkyl radicals and their brief mechanistic studies.展开更多
An enantioselective NiH-catalyzed hydroalkynylation ofα,β-unsaturated amides is reported.A wide range ofα,β-unsaturated amides and bromoalkynes are suitable substrates for this reaction,which proceeds under mild c...An enantioselective NiH-catalyzed hydroalkynylation ofα,β-unsaturated amides is reported.A wide range ofα,β-unsaturated amides and bromoalkynes are suitable substrates for this reaction,which proceeds under mild conditions,allowing access to a variety of enantioenriched chiralβ-alkynyl amides.β,γ-Unsaturated amides can also be used as substrates and undergo theβ-selective hydroalkynylation with a slightly lower enantiomeric excess.展开更多
A readily availableβ-sulfonamide alcohol-titanium complex was found to be effective on promoting the asymmetric addition reaction of an alkynylzinc reagent to unactivated simple ketones under very mild conditions.And...A readily availableβ-sulfonamide alcohol-titanium complex was found to be effective on promoting the asymmetric addition reaction of an alkynylzinc reagent to unactivated simple ketones under very mild conditions.And the corresponding chiral tertiary propargylic alcohols were obtained with enantiomeric excesses of up to 86%,which provided a simple,practical and inexpensive method to generate chiral tertiary propargylic alcohols.展开更多
A new cross-coupling reaction of N-benzylic sulfonamides with terminal alkynes for the synthesis of internal alkynes is reported.In the presence of 5 mol%of(Tf)_(2)NH/Bi(OTf)_(3)(1∶1),a broad range of N-benzylic sulf...A new cross-coupling reaction of N-benzylic sulfonamides with terminal alkynes for the synthesis of internal alkynes is reported.In the presence of 5 mol%of(Tf)_(2)NH/Bi(OTf)_(3)(1∶1),a broad range of N-benzylic sulfona-mides react smoothly with arylacetylenes to afford structurally diverse internal alkynes in moderate to excellent yields.We reasoned that vinyl cations could be formed by the regioselective attack of terminal alkynes with benzyl cations generated in situ from N-benzylic sulfonamides under acidic conditions,which then eliminated to form a carbon-carbon triple bond.展开更多
Alkynes are frequently found in a high proportion of natural products and bioactive moleculars,as well as a common synthon in organic synthesis,which can be easily transformed to an alkenyl,alkyl,heteroaryl,or carboxy...Alkynes are frequently found in a high proportion of natural products and bioactive moleculars,as well as a common synthon in organic synthesis,which can be easily transformed to an alkenyl,alkyl,heteroaryl,or carboxylic acid group.The enantioselective construction of alkyne substituted all carbon quaternary stereocenters is rarely reported and still a big challenge.As part of our continuous effort on developing asymmetric radical transformations,we found introducing an amidyl group(CONHAr)adjacent to the tertiary carbon radical could enable the asymmetric radical coupling with alkyne reagents.The amidyl group may stabilize the tertiary carbon radical or coordination with the chiral copper catalyst.Herein,we communicate a copper-catalyzed asymmetric trifluoromethyl-alkynylation ofα-aryl substituted acrylamides,which provides a straightforward and efficient access to chiral quaternary all-carbon centers bearing alkynyl groups in good yields and enantioselectivities.This reaction was also applied for the synthesis of chiral functionalized dipeptide.展开更多
Enhancing the sensitivity of nuclear magnetic resonance(NMR)technology has been the focus of NMR research for decades,which offers the potential to significantly expand its applications in chemistry,biology,and medica...Enhancing the sensitivity of nuclear magnetic resonance(NMR)technology has been the focus of NMR research for decades,which offers the potential to significantly expand its applications in chemistry,biology,and medical imaging.Parahydrogen-induced polarization(PHIP)emerges as a cost-effective approach to substantially enhance the sensitivity of NMR.Nevertheless,the amplification of the ^(1)H signal in PHIP is susceptible to interference from the thermal polarization state ^(1)H NMR signal.Employing RASER(radiofrequency amplification by stimulated emission of radiation)proves effective in mitigating such interference,which can reduce the linewidth and increase the sensitivity at the same time.In this work,we utilized PHIP and RASER to enhance the signal-to-noise ratio(SNR)of a series of biocompatible alkynyl organic acid molecules.The alkynyl acid with the highest enhancement factor was first identified through PASADENA(parahydrogen and synthesis allow dramatically enhanced nuclear alignment)experiments.Subsequently,RASER experiments were carried out through hyperpolarization of 5-hexynoic acid,exploring its signal characteristics under varying flow rates and pressures.The SNR of proton signals of 5-hexynoic acid surpassed 150,000,an 18.62-fold improvement compared with traditional hyperpolarized signals in PASADENA,and a markedly narrowed linewidth of 0.06 Hz.展开更多
Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is sti...Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is still lacking for understanding the structure-performance relationship at atomical level.Herein,we report the synthesis,structure analysis,and OER catalytic properties of a novel atomically precise Cu nanocluster of[Cu_(6)(C≡CR)4(dppe)3](R=Fe(C_(5)H_(5))_(2),abbreviated as Cu_(6)NC).Cu_(6)NC possesses a unique metal core configuration and metal-ligand binding motifs.Interestingly,Cu_(6)NC has superior OER performance to pure phosphine ligand-protected Cu18 nanocluster(Cu18NC in short,same Cu amount)and Cu nanoparticle(CuNP)with larger size,manifested by the lower overpotential at 10 mA·cm^(−2),smaller Tafel slope,and reduced charge transfer resistance.Cu_(6)NC also demonstrated excellent long-term stability for prolonged operation.Density functional theory(DFT)calculations further confirm that the alkynyl ligand plays a critical role in promoting the catalytic performance,and Cu_(6)NC has a lower energy barrier in the rate-determining step of the OER process.This study not only highlights the unique advantages of employing ultrasmall Cu nanoclusters for OER,but also can shed light on designing ligand-functionalized metal nanoclusters for electrochemical energy conversion and beyond.展开更多
A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed.This facile process tolerates a wide variety of functional groups,occurs at mild conditions in onepot procedure...A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed.This facile process tolerates a wide variety of functional groups,occurs at mild conditions in onepot procedure with short reaction time.The obtained mono-C-alkynyl-o-carboranes can be easily derivatized to synthesize 1,2-difunctionalized o-carboranes.This work provides a useful tool for the functionalization of o-carboranes.展开更多
基金supported financially by the Excellent Going Abroad Expert's Training Program in Hebei Province (No. 201940)the Hebei Natural Science Foundation of China (No. H2020208030)the S & T Program of Hebei (No. 22567607H) for financial support。
文摘A nickel-catalyzed C(sp^(2))–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the reaction step and atom economy. It has been investigated that the 2,4,6-trimethylpyridine ligand was critical to achieve the optimized reactivity. This protocol provides a straightforward route for synthesizing the alkynylated free benzylamines, featuring good substrate compatibility and monoselectivity.
基金the National Natural Science Foundation of China(Nos.22371273,22293011 and T2341001)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2023476)the National Science Foundation of Anhui Province(No.2208085J26)。
文摘Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp)-C(sp^(3))and C(sp)-C(sp^(2))bonds.This presented reaction has a broad substrate scope,enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl(pseudo)halides.This presented reaction is conducted under mild conditions,tolerating many functional groups,thus suitable for the modification and synthesis of biologically active molecules.
基金Financial support from the National Natural Science Foundation of China(No.22171145 to Z.Jin,32072440 to X.Xu)is gratefully acknowledged.
文摘Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring.Herein,with the assistance of a practical biaryl indolyl directing template,palladium-catalyzed remote sp^(2)C-H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity.Moreover,remote meta-selective C-H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst.These meta-C-H functionalized products proved to be the superior synthetic precursors,which are difficult to access using the conventional strategy.
基金supported financially by National Nature Science Foundation of China(No.22171258)the Youth Innovation Promotion Association CAS(No.2022375)+1 种基金the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008)the Sichuan Science and Technology Program(No.2022ZYD0038)。
文摘Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.
基金financial supported by the National Natural Science Foundation of China (No. 21722204)Fok Ying Tung Education Foundation (No. 151035)+1 种基金the Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Guangxi Normal University) (No. CHEMR2016-B09)Guangxi Funds for Distinguished expert
文摘Current synthesis of α-substituted 3,6-dihydro-2H-pyrans dominantly relies on functional group transformation. Herein, a direct and practical oxidative C -H alkynylation and alkenylation of 3,6-dihydro-2H-pyran skeletons with a range of potassium trifluoroborates is developed. The metal-free process is well tolerated with a wide variety of 3,6-dihydro-2H-pyrans, rapidly providing a library of 2,4-disubstituted 3,6-dihydro-2H-pyrans with diverse patterns of α-functionalities for further diversification and bioactive small molecule identification.
基金This study is supported by the National Natural Science Foundation of China(No.20472116)the Natural Science Foundation of Liaoning Province(No.1050155)Shenyang Pharmaceutical University Fund.
文摘Sciff bases 1 and 2, .which were derived from chiral aminoalcohols, were used as figands in Ti-catalyzed asymmetric alkynylation of aldehydes. Good enantioselectivities （up to 88% ee） and high chemical yields （80-90%） were obtained.
基金supported by the Natural Science Foundation of Shandong Province(ZR2019BB011)the Scientific Research Foundation of Qingdao University of Science&Technology(010029022).
文摘A new,selective Ru(Ⅱ)-catalyzed alkynylation reaction of isoquinolones,quinazolones and phthalazinones with readily available bromoalkynes has been developed.This reaction enables the selective construction of a new C(sp^(2))-C(sp)bond through C-H activation and C-Br functionalization,and offers an effective and selective route to synthesizing highly valuable alkynylated isoquinolone,quinazolone and phthalazinonederivatives with a wide substrate scope and highselectivity.
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21702103 and 21522604)the Jiangsu Synergetic Innovation Center for Advanced Bio-Manufacture(No.XTD2203)the Natural Science Research Projects of Jiangsu Higher Education(No.19KJB150027).
文摘A green efficient photoredox-catalyzed decarboxylative alkynylation of carboxylic acids with alkynyl bromides has been developed.This broadly applicable protocol is presented whereinα-amino,aliphatic andα-oxy acids are converted into useful alkynylation products.The commercially-available organic photocatalyst 4CzIPN is used as the photocatalyst,organic base DBU is utilized as the base,and DMSO serves as solvent.This strategy features mild conditions,is metal-free,and is environmentally friendly.The batch and continuous-flow protocols described were applied to obtain a broader substrate scope of functionalization(more than 50 examples).Furthermore,we demonstrate that the use of microflow technology enhanced and intensified the reaction process,achieving significantly reduced reaction times(i.e.,10 min of residence time).
基金support of this work by the National Natural Science Foundation of China(Nos.22371307,21971267)the program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07C069).
文摘Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(sp^(3))-F bonds functionalization have been greatly developed,catalytic cross-coupling of trifluoromethylarenes with C-H of terminal alkynes remains a challenge.Here,we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis.Tridentate anionic ligand is pivotal to realize this C-H sp-sp^(3) cross-coupling.Moreover,this unique catalytic system is also suitable for cross-coupling of C(sp^(3))-F bonds with azoles C(sp^(2))-H bonds.A series of trifluoromethylarenes,terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products.Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.
基金Financial support from the program of the National Natural Science Foundation of China(No.21871086,Y.-Q.Z.)is gratefully acknowledged.
文摘The highly stereoselective synthesis of diverse medicinally valuable alkynyl C-glycosides under mild and green reaction conditions remains a great challenge.Herein,we wish to report a visible-light induced photocatalytic decarboxylative alkynylation approach.By utilizing an iridium photocatalyst in the presence of visible light,glycosyl radicals are in-situ generated via the decarboxylation of anomeric acids and efficiently coupled with a variety of ethynylbenziodoxolones(EBXs),which allows the facile synthesis of a variety of alkynyl C-glycosides in moderate to high yields and with excellent diastereoselectivity.
基金supported by the Research Grants Council of The Hong Kong Special Administration Region(14304115,14305017)CUHK Direct Grant and Incentive Grant from Faculty of Science,CUHK
文摘Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords unprecedented C,B-substituted carborane-fused-pyridone derivatives, whereas the use of terminal alkynes leads to B–H/C(sp)–H dehydrocoupling products. The isolation and structural identification of a notably stable Cu(Ⅰ) intermediate shed light on the reaction mechanism, which is proposed to involve a Cu(Ⅲ) intermediate.
基金supported by NSFC(22371008),BNLMSLaboratory for Synthetic Chemistry and Chemical Biology of Health@InnoHK of ITC,HKSAR.
文摘Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes.This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups.Mechanistically,the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation.The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.
基金We are grateful to the National Natural Science Foundation of China(22071073,22271112,21772218,and 21821002)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences and the Central China Normal University(CCNU).
文摘Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for the construction of chiral alkynes.The asymmetric C(sp^(3))–C(sp)cross-coupling provides a significant complementary strategy through radical-initiated process.However,the stereocontrol of highly reactive and unstable radical intermediate has been a challenge for decades.To address this problem,a variety of chiral ligands are developed for initiating the reaction and achieving enantiocontrol of alkyl radicals.This review summarizes recent developments in copper-catalyzed enantioselective alkynylation of prochiral alkyl radicals and their brief mechanistic studies.
基金We thank the financial support from the Natural Science Foundation of Jiangsu Province(No.BK20190281).
文摘An enantioselective NiH-catalyzed hydroalkynylation ofα,β-unsaturated amides is reported.A wide range ofα,β-unsaturated amides and bromoalkynes are suitable substrates for this reaction,which proceeds under mild conditions,allowing access to a variety of enantioenriched chiralβ-alkynyl amides.β,γ-Unsaturated amides can also be used as substrates and undergo theβ-selective hydroalkynylation with a slightly lower enantiomeric excess.
基金suported by the National Natural Science Foundation of China(Nos.20372028,20472026,20525206,20021001)the Specialized Research Fund for the Doctoral Program in Higher Education Institutions of the Ministry of Education of China.
文摘A readily availableβ-sulfonamide alcohol-titanium complex was found to be effective on promoting the asymmetric addition reaction of an alkynylzinc reagent to unactivated simple ketones under very mild conditions.And the corresponding chiral tertiary propargylic alcohols were obtained with enantiomeric excesses of up to 86%,which provided a simple,practical and inexpensive method to generate chiral tertiary propargylic alcohols.
基金We are grateful for the financial support from the National Natural Science Foundation of China(No.21202154)NJIT Scientific Research Foundation for Introducing Talents(No.YKJ201329),Nanjing Institute of Technology and the University of Science and Tech-nology of China.
文摘A new cross-coupling reaction of N-benzylic sulfonamides with terminal alkynes for the synthesis of internal alkynes is reported.In the presence of 5 mol%of(Tf)_(2)NH/Bi(OTf)_(3)(1∶1),a broad range of N-benzylic sulfona-mides react smoothly with arylacetylenes to afford structurally diverse internal alkynes in moderate to excellent yields.We reasoned that vinyl cations could be formed by the regioselective attack of terminal alkynes with benzyl cations generated in situ from N-benzylic sulfonamides under acidic conditions,which then eliminated to form a carbon-carbon triple bond.
基金financial support from the National Key R&D Program of China(No.2021YFA1500100)the National Na-ture Science Foundation of China(Nos.91956202,21790330,and 21821002)+2 种基金the Science and Technology Commission of Shanghai Municipality(NoS.20JC1417000,21520780100,and19590750400)the Key Research Program of Frontier Science(QYZDJSSW-SLH055)the International Partnership Program(121731KYSB20190016)of the Chinese Academy of Sciences.
文摘Alkynes are frequently found in a high proportion of natural products and bioactive moleculars,as well as a common synthon in organic synthesis,which can be easily transformed to an alkenyl,alkyl,heteroaryl,or carboxylic acid group.The enantioselective construction of alkyne substituted all carbon quaternary stereocenters is rarely reported and still a big challenge.As part of our continuous effort on developing asymmetric radical transformations,we found introducing an amidyl group(CONHAr)adjacent to the tertiary carbon radical could enable the asymmetric radical coupling with alkyne reagents.The amidyl group may stabilize the tertiary carbon radical or coordination with the chiral copper catalyst.Herein,we communicate a copper-catalyzed asymmetric trifluoromethyl-alkynylation ofα-aryl substituted acrylamides,which provides a straightforward and efficient access to chiral quaternary all-carbon centers bearing alkynyl groups in good yields and enantioselectivities.This reaction was also applied for the synthesis of chiral functionalized dipeptide.
基金supported by the National Natural Science Foundation of China(grant number:22274050)the Shanghai Science and Technology Commission(contract number:23J21900300)the Fundamental Research Funds for the Central Universities.
文摘Enhancing the sensitivity of nuclear magnetic resonance(NMR)technology has been the focus of NMR research for decades,which offers the potential to significantly expand its applications in chemistry,biology,and medical imaging.Parahydrogen-induced polarization(PHIP)emerges as a cost-effective approach to substantially enhance the sensitivity of NMR.Nevertheless,the amplification of the ^(1)H signal in PHIP is susceptible to interference from the thermal polarization state ^(1)H NMR signal.Employing RASER(radiofrequency amplification by stimulated emission of radiation)proves effective in mitigating such interference,which can reduce the linewidth and increase the sensitivity at the same time.In this work,we utilized PHIP and RASER to enhance the signal-to-noise ratio(SNR)of a series of biocompatible alkynyl organic acid molecules.The alkynyl acid with the highest enhancement factor was first identified through PASADENA(parahydrogen and synthesis allow dramatically enhanced nuclear alignment)experiments.Subsequently,RASER experiments were carried out through hyperpolarization of 5-hexynoic acid,exploring its signal characteristics under varying flow rates and pressures.The SNR of proton signals of 5-hexynoic acid surpassed 150,000,an 18.62-fold improvement compared with traditional hyperpolarized signals in PASADENA,and a markedly narrowed linewidth of 0.06 Hz.
基金supported by Guangdong Natural Science Funds(No.2023A0505050107)Hong Kong Research Grant Council General Research Fund(Nos.16201820 and 16201622)+1 种基金Green Tech Fund(No.GTF202020131)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(No.HZQB-KCZYB-2020083).
文摘Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is still lacking for understanding the structure-performance relationship at atomical level.Herein,we report the synthesis,structure analysis,and OER catalytic properties of a novel atomically precise Cu nanocluster of[Cu_(6)(C≡CR)4(dppe)3](R=Fe(C_(5)H_(5))_(2),abbreviated as Cu_(6)NC).Cu_(6)NC possesses a unique metal core configuration and metal-ligand binding motifs.Interestingly,Cu_(6)NC has superior OER performance to pure phosphine ligand-protected Cu18 nanocluster(Cu18NC in short,same Cu amount)and Cu nanoparticle(CuNP)with larger size,manifested by the lower overpotential at 10 mA·cm^(−2),smaller Tafel slope,and reduced charge transfer resistance.Cu_(6)NC also demonstrated excellent long-term stability for prolonged operation.Density functional theory(DFT)calculations further confirm that the alkynyl ligand plays a critical role in promoting the catalytic performance,and Cu_(6)NC has a lower energy barrier in the rate-determining step of the OER process.This study not only highlights the unique advantages of employing ultrasmall Cu nanoclusters for OER,but also can shed light on designing ligand-functionalized metal nanoclusters for electrochemical energy conversion and beyond.
基金financial support from the National Natural Science Foundation of China(Nos.21672193,21272218)the Key Scientific and Technological Project of Henan Province(No.202102310327)+3 种基金the Ministry of Industry and Information Technology(No.Z135060009002)the Postdoctoral Research Grant in Henan Province(No.001803004)the Programme of Introducing Talents of Discipline to Universities(111 Project,No.D20003)Zhengzhou University of China。
文摘A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed.This facile process tolerates a wide variety of functional groups,occurs at mild conditions in onepot procedure with short reaction time.The obtained mono-C-alkynyl-o-carboranes can be easily derivatized to synthesize 1,2-difunctionalized o-carboranes.This work provides a useful tool for the functionalization of o-carboranes.
