Two organic dyes XSS1 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar ceils （DSCs） employing cobalt and iodine redox shuttles. The effects of dye structure upon the photoph...Two organic dyes XSS1 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar ceils （DSCs） employing cobalt and iodine redox shuttles. The effects of dye structure upon the photophysical, electro-chemical characteristics and cell perfor- mance are investigated. XS51 with four hexyloxyl groups on triarylamine performs better steric hindrance and an improvement of photovoltage. X852 provides higher short-circuit photocurrent density due to the strong electron-donating capability of indoline unit. The results from the redox electrolyte on cell performances indicate that the synthesized dyes are more suitable for tris（1,10-phenanthroline）cobalt（II/III） redox couple than I-/I3- redox couple in assembling DSCs. Application of X852 in the cobalt electrolyte yields a DSC with an overall power conversion efficiency of 6.58% under AM 1.5 （100 mW/cm2） irradiation.展开更多
We report a 2-iodoxybenzoic acid(IBX)-mediated intarmolecular oxidative spiro-fused tandem cyclization reaction of tryptophan analogs bearing an N-arylamides side-chain to rapidly afford polycyclic spiroindolines feat...We report a 2-iodoxybenzoic acid(IBX)-mediated intarmolecular oxidative spiro-fused tandem cyclization reaction of tryptophan analogs bearing an N-arylamides side-chain to rapidly afford polycyclic spiroindolines featuring multiple stereocenters including a quaternary stereocenters under mild reaction conditions.Among them,a novelty azaphosphol idine-containing spiroindoline compound is synthesized for the first time.It may open the door to azaphos pholidine-containing spiroindoline compound of potential interest in synthetic and medicinal chemistry.A plausible mechanism is proposed.展开更多
We herein report a highly regioselective rhodium-catalyzed C6-and C7—H bond functionalization of indolines with alkynes by using 2-pyrimidine as a directing group. Moreover, NH-free benzo[g]indole unit could be obtai...We herein report a highly regioselective rhodium-catalyzed C6-and C7—H bond functionalization of indolines with alkynes by using 2-pyrimidine as a directing group. Moreover, NH-free benzo[g]indole unit could be obtained by an oxidation/removal of the directing group sequence.展开更多
Thermodynamic and kinetic properties of the tautomerism of an indoline spiropyran in compressed CO2-ethanol mixture were studied by UV-Vis spectroscopy at 298.15 K, 303. 15 K, and 308.15 K. It was found that the compo...Thermodynamic and kinetic properties of the tautomerism of an indoline spiropyran in compressed CO2-ethanol mixture were studied by UV-Vis spectroscopy at 298.15 K, 303. 15 K, and 308.15 K. It was found that the composition of the mixture affects the equilibrium constant and the rate constant significantly.展开更多
Enantiomerically pure 2-substituted indolines are an important class of nitrogen heterocycles that occur frequently in many alkaloid natural products and biologically active compounds.Consequently,the synthesis of suc...Enantiomerically pure 2-substituted indolines are an important class of nitrogen heterocycles that occur frequently in many alkaloid natural products and biologically active compounds.Consequently,the synthesis of such skeletons is of great significance.The past years have witnessed a number of remarkable advances in the development of efficient strategies to construct this class of chiral compounds.This review summarizes the recent advances in asymmetric synthesis of 2-substituted indoline derivatives.Due to the limitation of the length,this review only summarizes those works published from January of 2012 to January of 2019.Meanwhile,methods towards synthesis of fu sed and spirocyclic indolines will not be discussed in this review.展开更多
Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods. Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye-se...Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods. Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye-sensitized solar cells revealed： （i） as the number of rhodanine rings increases, the energy difference between HOMO and LUMO decreases and there is a red shift in the absorption spectrum with the binding energy increased, and the transition dipole moment decreased; （ii） Based on an analysis of charge differential density, we observed that the charge and energy are transfered from the phenylethenyl to the indoline and rhodanine rings; （iii） The electron-hole coherences are mainly on the indoline and rhodanine rings, and the exciton sizes are 30 and 40 atoms for indoline dyes with one and two rhodanline rings, respectively. These results serve as a good example of computer-aided design in metal-free indoline dyes for dye-sensitized solar cells.展开更多
An electrochemical amino-azidation of 2-aminostyre ne with sodium azide(NaN3)was developed,which can be carried out smoothly in water under metal-free condition,affording a series of 3-azido indolines with high yields.
Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy...Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy fabrication. Three D—A—D—A type organic semiconductors(WS-31,WS-32 and WS-52) are synthesized, based on the indoline donor and benzotriazole auxiliary acceptor core, along with either bare thiophene or rigid cyclopentadithiophene as π bridge, rhodanine or carbonocyanidate as end-group. Their HOMO orbitals are delocalized throughout the whole molecules. Whereas the LUMOs are mainly localized on the acceptor part of structure, which reach up to benzothiadiazole, but no distribution on indoline donor. The first excitations for WS-31 and WS-32 are mainly originated by electron transition from HOMO to LUMO level, while for WS-52, partly related to transition between HOMO and LUMO+1 level. The small organic molecules are applied as donor components in bulk heterojunction(BHJ) organic solar cells, using PC_(61)BM as acceptor material to check their photovoltaic performances. The BHJ solar cells based on blended layer of WS-31:PC_(61)BM and WS-32:PC_(61)BM processed with chloroform show overall photoelectric conversion efficiency(PCE) of 0.56% and 1.02%, respectively. WS-32 based BHJ solar cells show a higher current density originated by its relatively larger driving force of photo-induced carrier in photo-active layer to LUMO of PC_(61)BM.展开更多
The dye sensitized solar cells (DSSCs) have been extensively studied due to their low production cost and simple fabrication process. Dye co-sensitization broadens the absorption spectrum of the sensitizer;thus enhanc...The dye sensitized solar cells (DSSCs) have been extensively studied due to their low production cost and simple fabrication process. Dye co-sensitization broadens the absorption spectrum of the sensitizer;thus enhances light harvesting efficiency;and contributes to the improvement of the DSSCs overall efficiency. In this study we performed theoretical design of complex molecule (C45H32N2O4) through combination (esterification reaction) of the natural dye lawsone and synthetic metal free indoline dye D131. The excitation energies, vibration spectra, molecular structures, electronic absorption spectra and electron transitions in individual dyes and complex molecule were investigated using density functional theory (DFT) and time dependent density functional theory (TD-DFT) B3LYP5 methods, with 3-21G, 6-31G and 6-31G(d,p) basis sets. The UV-Vis absorption spectra of the individual dyes and their mixture in chloroform solution were measured using spectrophotometer. For the complex formation reaction, enthalpy, entropy and Gibbs free energy were calculated and the results indicated the reaction was endothermic and non-spontaneous. Electron density distribution of the frontier and adjacent molecular orbitals and energy levels alignment were used for analysis of the electronic spectra and mechanism of transitions. The results indicated that the designed complex molecule satisfied the requirements for good photosensitizer of DSSCs.展开更多
An efficiently catalytic method toward the synthesis of indolin-2-ones featuring an allylic derived C_(3)-quaternary stereocenter via an intramolecular Heck cyclization/Suzuki coupling of N-substituted-N-(2-bromopheny...An efficiently catalytic method toward the synthesis of indolin-2-ones featuring an allylic derived C_(3)-quaternary stereocenter via an intramolecular Heck cyclization/Suzuki coupling of N-substituted-N-(2-bromophenyl)acrylamides and organoboron reagents was successfully developed by using a 1,3-bis(2,6-diisopropylphenyl)acenaphthoimidazol-2-ylidene(AnIPr)-ligated oxazoline palladacycle.It enabled a very broad substrate scope tolerating different functional groups,electronic properties and steric bulkiness.Notably,it revealed a great potential to build diverse heterocycle-fused indoline alkaloids via the same intermediate 3-allyl-1,3-dimethylindolin-2-one.展开更多
A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR pr...A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR protocol lies in the utilization of chiral phosphoric acid-catalyzed triazane formation reaction with azodicarboxylates, which enables the enantioselective synthesis of various substituted indolines bearing C3-quaternary stereocenters with good to high enantioselectivities(with sfactors up to 70). Moreover, an intriguing parallel kinetic resolution(PKR) has been developed by combining triazane formation and dehydrogenation reactions using different azodicarboxylates. Experimental studies have provided insight into the mechanism of this PKR reaction, demonstrating stereoselectivity in both triazane formation and dehydrogenation steps, favoring the opposite enantiomers. The large-scale synthesis and diverse derivatizations of the products, particularly the imine groupcontaining 3H-indoles, demonstrate the value of these(P)KR methods.展开更多
The cooperative visible-light mediated and NHC-catalyzed dearomative arylation-acylation of N-(2-bromobenzoyl)indoles with aldehydes was developed, affording the corresponding highly functionalized polycyclic indoline...The cooperative visible-light mediated and NHC-catalyzed dearomative arylation-acylation of N-(2-bromobenzoyl)indoles with aldehydes was developed, affording the corresponding highly functionalized polycyclic indolines in moderate to good yields with exclusive diastereoselectivities. Mechanism investigations support the activation of CAr-Br bond via visible-light mediated energy transfer(EnT) and the following single-electron-transfer(SET) with Breslow intermediate under NHC catalysis to give key aryl radical and ketyl radical. This protocol demonstrates the cleavage of CAr-Br bond under mild cooperative EnT/NHC catalysis.展开更多
An electrochemical synthesis of functionalized （aza）indolines through dehydrogenative [3＋2] annulation of arylamines with tethered alkenes has been developed. Previous reported syntheses through similar inter- and ...An electrochemical synthesis of functionalized （aza）indolines through dehydrogenative [3＋2] annulation of arylamines with tethered alkenes has been developed. Previous reported syntheses through similar inter- and intramolecular annulation reactions required noble-metal catalysts and are mostly limited to terminal alkenes or 1,3-dienes. The electrosynthesis employs the easily available and inexpensive ferrocene as the molecular catalyst and is compatible with di-, tri- and even tetrasubstituted alkenes to construct indolines as well as the more challenging azaindolines. Employing the newly developed electrosynthesis as a key step, the total synthesis of marine alkaloid （＋）-hinckdentine A has been achieved in 12 steps （longest linear sequence） from commercially available materials.展开更多
Summary of main observation and conclusion A 4+2 cycloaddition reaction of NH-free benzazetidines with indoles under the catalysis of camphorsulfonic acid was developed. This method shows a broad substrate scope of be...Summary of main observation and conclusion A 4+2 cycloaddition reaction of NH-free benzazetidines with indoles under the catalysis of camphorsulfonic acid was developed. This method shows a broad substrate scope of benzazetidines and indoles, and offers a convenient method for stereoselective synthesis of various cis-2,3-fused indoline aminals. Preliminary mechanistic studies suggest the reaction proceed via a stepwise pathway featuring an electrophilic attack on the benzylic carbon of benzazetidine.展开更多
A convergent construction of [2,3]-fused indoline tetrahydropyridazines via an I2/tert-butyl hydroperoxide(TBHP) catalyzed three-component dearomative oxidative coupling of indoles, hydrazines and acetophenone was est...A convergent construction of [2,3]-fused indoline tetrahydropyridazines via an I2/tert-butyl hydroperoxide(TBHP) catalyzed three-component dearomative oxidative coupling of indoles, hydrazines and acetophenone was established in moderate to good yields. This protocol provides a new approach for the synthesis of these biologically interesting fused indolines.展开更多
We report herein a palladium-catalyzed diarylative dearomatization of indole by employing thioester and arylboronic acid as the aryl electrophiles.The reaction involved a decarbonylation/migratory insertion/terminal S...We report herein a palladium-catalyzed diarylative dearomatization of indole by employing thioester and arylboronic acid as the aryl electrophiles.The reaction involved a decarbonylation/migratory insertion/terminal Suzuki coupling procedure.Substrates bearing various functional groups are well tolerated in the reaction,affording the diarylated indoline skeletons in moderate to good yields.展开更多
Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region.Two indoline D-A-π-A motif sensitizers(WS-2 and WS-39) that possess...Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region.Two indoline D-A-π-A motif sensitizers(WS-2 and WS-39) that possess similar light response area but distinctly reversed feature in photovoltaic performance are selected as the specific cosensitization couple. That is, WS-2 shows quite high photocurrent but low photovoltage, and WS-39 gives relatively low photocurrent but quite high photo voltage. Due to the obvious "barrel effect",both dyes show medium PCE around8.50%. In contrast with the previous cosensitization strategy mostly focused on the compensation of light response region, herein we perform different cosensitization sequence, for taking insight into the balance of photocurrent and photo voltage, and achieving the synergistic improvement in power conversion efficiency(PCE). Electronic impedance spectra(EIS) indicate that exploiting dye WS-39 with high V_(OC) value as the primary sensitizer can repress the charge recombination more effectively, resulting in superior V_(OC) rather than using dye WS-2 with high J_(SC)as the primary sensitizer. As a consequence, a high PCE value of 9.48% is obtained with the delicate cosensitization using WS-39 as primary dye and WS-2 as accessory dye, which is higher than the corresponding devices sensitized by each individual dye(around 8.48-8.67%). It provides an effective optimizing strategy of cosensitization how to combine the individual dye advantages for developing highly efficient solar cells.展开更多
The copper-catalyzed directed dearomatization of indoles with the assistance of directing groups has been developed for the synthesis of 2,3-diazido indolines with good yields and excellent diastereoselectivities in a...The copper-catalyzed directed dearomatization of indoles with the assistance of directing groups has been developed for the synthesis of 2,3-diazido indolines with good yields and excellent diastereoselectivities in aqueous solution.The resultant 2,3-diazides can be smoothly converted to other functional groups,including vicinal diamines,triazoles and benzotriazoles,in a single step.展开更多
Functional organic dyes have promising prospect in dye-sensitized solar cells as a crucial element, of which sensitizers based on donor-π-acceptor are the most important dyes. On the basis of the structures of the ar...Functional organic dyes have promising prospect in dye-sensitized solar cells as a crucial element, of which sensitizers based on donor-π-acceptor are the most important dyes. On the basis of the structures of the aromatic amine donors such as triphenylamine and indoline, this paper reviews the photoelectric conversion properties of organic sensitizers since 2008, and highlights research work in our laboratory in this area.展开更多
Transition metal-catalyzed asymmetric hydrogenation(AH)of unprotected indoles has mainly been applied to alkyl substituted unprotected indoles.However,the challenging aryl substituted unprotected indoles with poor rea...Transition metal-catalyzed asymmetric hydrogenation(AH)of unprotected indoles has mainly been applied to alkyl substituted unprotected indoles.However,the challenging aryl substituted unprotected indoles with poor reactivity and enantioselectivity(≤42%ee)could not be hydrogenated well.In this work,a highly efficient Ir/bisphosphine-thiourea ligand ZhaoPhos catalytic system for the AH of challenging aryl substituted unprotected indoles has been successfully developed for the first time with high reactivity and excellent stereoselective control.Moreover,a series of 2-alkyl-substituted and 2,3-disubstituted unprotected indoles were also well tolerated in this catalytic system.A wide variety of chiral indoline derivatives were obtained in good to high yields with excellent stereoselectivities(75–99%yields,>20:1 dr,and 86–99%ee).The anion-binding activation strategy played an important role in accessing both high reactivity and excellent stereoselectivity,which was formed between the catalyst and unprotected indoles in situ-generating iminium ion with the assistance of Brønsted acid.A possible catalytic mechanism was proposed for this Ir-catalyzed AH according to density functional theory calculations and control experiment results.Readily available substrates,a broad range of substrate tolerance,an efficient chiral catalytic system,and a gram-scale protocol further demonstrated the potential practicality of this methodology.展开更多
文摘Two organic dyes XSS1 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar ceils （DSCs） employing cobalt and iodine redox shuttles. The effects of dye structure upon the photophysical, electro-chemical characteristics and cell perfor- mance are investigated. XS51 with four hexyloxyl groups on triarylamine performs better steric hindrance and an improvement of photovoltage. X852 provides higher short-circuit photocurrent density due to the strong electron-donating capability of indoline unit. The results from the redox electrolyte on cell performances indicate that the synthesized dyes are more suitable for tris（1,10-phenanthroline）cobalt（II/III） redox couple than I-/I3- redox couple in assembling DSCs. Application of X852 in the cobalt electrolyte yields a DSC with an overall power conversion efficiency of 6.58% under AM 1.5 （100 mW/cm2） irradiation.
基金the National Natural Science Foundation of China(Nos.U1604285,21772032 and 21702051)Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT)of Ministry of Education of China(No.IRT1061)+3 种基金the 111 Project(No.D17007)Henan Provincial Natural Science Foundation(No.162300410180)Key Project of Henan Educational Committee(No.18A150009)Program for Innovative Research Team of Science and Technology in the University of Henan Province(No.18IRTSTHN004)。
文摘We report a 2-iodoxybenzoic acid(IBX)-mediated intarmolecular oxidative spiro-fused tandem cyclization reaction of tryptophan analogs bearing an N-arylamides side-chain to rapidly afford polycyclic spiroindolines featuring multiple stereocenters including a quaternary stereocenters under mild reaction conditions.Among them,a novelty azaphosphol idine-containing spiroindoline compound is synthesized for the first time.It may open the door to azaphos pholidine-containing spiroindoline compound of potential interest in synthetic and medicinal chemistry.A plausible mechanism is proposed.
基金supported by the National Natural Science Foundation of China (Nos. 21602064 and 21572072)the Natural Science Foundation of Fujian Province (No. 2015J01056)Huaqiao University (No. ZQN-PY317)
文摘We herein report a highly regioselective rhodium-catalyzed C6-and C7—H bond functionalization of indolines with alkynes by using 2-pyrimidine as a directing group. Moreover, NH-free benzo[g]indole unit could be obtained by an oxidation/removal of the directing group sequence.
文摘Thermodynamic and kinetic properties of the tautomerism of an indoline spiropyran in compressed CO2-ethanol mixture were studied by UV-Vis spectroscopy at 298.15 K, 303. 15 K, and 308.15 K. It was found that the composition of the mixture affects the equilibrium constant and the rate constant significantly.
基金National Natural Science Foundation of China(Nos.21702121,91856119 and 21622201)the Science and Technology Department of Hubei Province(Nos.2016CFA050 and 2017AHB047)the Program of Introducing Talents of Discipline to Universities of China(111 Program,No.B17019)。
文摘Enantiomerically pure 2-substituted indolines are an important class of nitrogen heterocycles that occur frequently in many alkaloid natural products and biologically active compounds.Consequently,the synthesis of such skeletons is of great significance.The past years have witnessed a number of remarkable advances in the development of efficient strategies to construct this class of chiral compounds.This review summarizes the recent advances in asymmetric synthesis of 2-substituted indoline derivatives.Due to the limitation of the length,this review only summarizes those works published from January of 2012 to January of 2019.Meanwhile,methods towards synthesis of fu sed and spirocyclic indolines will not be discussed in this review.
基金ACKN0WLEDGMENT This work was supported by the National Nature Science Foundation of China （No.10374040）.
文摘Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods. Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye-sensitized solar cells revealed： （i） as the number of rhodanine rings increases, the energy difference between HOMO and LUMO decreases and there is a red shift in the absorption spectrum with the binding energy increased, and the transition dipole moment decreased; （ii） Based on an analysis of charge differential density, we observed that the charge and energy are transfered from the phenylethenyl to the indoline and rhodanine rings; （iii） The electron-hole coherences are mainly on the indoline and rhodanine rings, and the exciton sizes are 30 and 40 atoms for indoline dyes with one and two rhodanline rings, respectively. These results serve as a good example of computer-aided design in metal-free indoline dyes for dye-sensitized solar cells.
基金financial support from the National Natural Science Foundation of China(Nos.21672200,21772185,21801233)the assistance of the product characterization from the Chemistry Experiment Teaching Center of University of Science and Technology of China+1 种基金supported by China Postdoctoral Science Foundation(No.2018M632532)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)。
文摘An electrochemical amino-azidation of 2-aminostyre ne with sodium azide(NaN3)was developed,which can be carried out smoothly in water under metal-free condition,affording a series of 3-azido indolines with high yields.
基金supported by the NSFC for Creative Research Groups(21421004)Distinguished Young Scholars(21325625)+4 种基金NSFC/China,Science and Technology Commission of Shanghai Municipality(14YF1410500 and 15XD1501400)Shanghai Young Teacher Supporting Foundation(ZZEGD14011)Program for Professor of Special Appointment(Eastern Scholar)"Shu Guang" project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(13SG55)Grants of computing timeat the C3SE supercomputing Center at Chalmers(Gteborg)
文摘Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy fabrication. Three D—A—D—A type organic semiconductors(WS-31,WS-32 and WS-52) are synthesized, based on the indoline donor and benzotriazole auxiliary acceptor core, along with either bare thiophene or rigid cyclopentadithiophene as π bridge, rhodanine or carbonocyanidate as end-group. Their HOMO orbitals are delocalized throughout the whole molecules. Whereas the LUMOs are mainly localized on the acceptor part of structure, which reach up to benzothiadiazole, but no distribution on indoline donor. The first excitations for WS-31 and WS-32 are mainly originated by electron transition from HOMO to LUMO level, while for WS-52, partly related to transition between HOMO and LUMO+1 level. The small organic molecules are applied as donor components in bulk heterojunction(BHJ) organic solar cells, using PC_(61)BM as acceptor material to check their photovoltaic performances. The BHJ solar cells based on blended layer of WS-31:PC_(61)BM and WS-32:PC_(61)BM processed with chloroform show overall photoelectric conversion efficiency(PCE) of 0.56% and 1.02%, respectively. WS-32 based BHJ solar cells show a higher current density originated by its relatively larger driving force of photo-induced carrier in photo-active layer to LUMO of PC_(61)BM.
文摘The dye sensitized solar cells (DSSCs) have been extensively studied due to their low production cost and simple fabrication process. Dye co-sensitization broadens the absorption spectrum of the sensitizer;thus enhances light harvesting efficiency;and contributes to the improvement of the DSSCs overall efficiency. In this study we performed theoretical design of complex molecule (C45H32N2O4) through combination (esterification reaction) of the natural dye lawsone and synthetic metal free indoline dye D131. The excitation energies, vibration spectra, molecular structures, electronic absorption spectra and electron transitions in individual dyes and complex molecule were investigated using density functional theory (DFT) and time dependent density functional theory (TD-DFT) B3LYP5 methods, with 3-21G, 6-31G and 6-31G(d,p) basis sets. The UV-Vis absorption spectra of the individual dyes and their mixture in chloroform solution were measured using spectrophotometer. For the complex formation reaction, enthalpy, entropy and Gibbs free energy were calculated and the results indicated the reaction was endothermic and non-spontaneous. Electron density distribution of the frontier and adjacent molecular orbitals and energy levels alignment were used for analysis of the electronic spectra and mechanism of transitions. The results indicated that the designed complex molecule satisfied the requirements for good photosensitizer of DSSCs.
基金National Natural Science Foundation of China(No.22101133)Natural Science Foundation of Jiangsu Province(No.BK20200768)and Nanjing Forestry University are greatly acknowledged.
文摘An efficiently catalytic method toward the synthesis of indolin-2-ones featuring an allylic derived C_(3)-quaternary stereocenter via an intramolecular Heck cyclization/Suzuki coupling of N-substituted-N-(2-bromophenyl)acrylamides and organoboron reagents was successfully developed by using a 1,3-bis(2,6-diisopropylphenyl)acenaphthoimidazol-2-ylidene(AnIPr)-ligated oxazoline palladacycle.It enabled a very broad substrate scope tolerating different functional groups,electronic properties and steric bulkiness.Notably,it revealed a great potential to build diverse heterocycle-fused indoline alkaloids via the same intermediate 3-allyl-1,3-dimethylindolin-2-one.
基金supported by the National Natural Science Foundation of China(22171186,22222107)ShanghaiTech University Start-up FundingAnalytical Instrumentation Center(#SPSTAIC10112914),SPST,ShanghaiTech University。
文摘A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR protocol lies in the utilization of chiral phosphoric acid-catalyzed triazane formation reaction with azodicarboxylates, which enables the enantioselective synthesis of various substituted indolines bearing C3-quaternary stereocenters with good to high enantioselectivities(with sfactors up to 70). Moreover, an intriguing parallel kinetic resolution(PKR) has been developed by combining triazane formation and dehydrogenation reactions using different azodicarboxylates. Experimental studies have provided insight into the mechanism of this PKR reaction, demonstrating stereoselectivity in both triazane formation and dehydrogenation steps, favoring the opposite enantiomers. The large-scale synthesis and diverse derivatizations of the products, particularly the imine groupcontaining 3H-indoles, demonstrate the value of these(P)KR methods.
基金supported by the National Natural Science Foundation of China(22071253,21831008)the Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202003)。
文摘The cooperative visible-light mediated and NHC-catalyzed dearomative arylation-acylation of N-(2-bromobenzoyl)indoles with aldehydes was developed, affording the corresponding highly functionalized polycyclic indolines in moderate to good yields with exclusive diastereoselectivities. Mechanism investigations support the activation of CAr-Br bond via visible-light mediated energy transfer(EnT) and the following single-electron-transfer(SET) with Breslow intermediate under NHC catalysis to give key aryl radical and ketyl radical. This protocol demonstrates the cleavage of CAr-Br bond under mild cooperative EnT/NHC catalysis.
文摘An electrochemical synthesis of functionalized （aza）indolines through dehydrogenative [3＋2] annulation of arylamines with tethered alkenes has been developed. Previous reported syntheses through similar inter- and intramolecular annulation reactions required noble-metal catalysts and are mostly limited to terminal alkenes or 1,3-dienes. The electrosynthesis employs the easily available and inexpensive ferrocene as the molecular catalyst and is compatible with di-, tri- and even tetrasubstituted alkenes to construct indolines as well as the more challenging azaindolines. Employing the newly developed electrosynthesis as a key step, the total synthesis of marine alkaloid （＋）-hinckdentine A has been achieved in 12 steps （longest linear sequence） from commercially available materials.
基金the National Natural Science Foundation of China (Nos. 21502098, 21672105)the Natural Science Foundation of Tianjin (17JCYBJC19700)the Qindao National Laboratory for Marine Scie nee and Tech no logy, and the State Key Laboratory of Elemento-Organic Chemistry at Nankai University for financial support of this work.
文摘Summary of main observation and conclusion A 4+2 cycloaddition reaction of NH-free benzazetidines with indoles under the catalysis of camphorsulfonic acid was developed. This method shows a broad substrate scope of benzazetidines and indoles, and offers a convenient method for stereoselective synthesis of various cis-2,3-fused indoline aminals. Preliminary mechanistic studies suggest the reaction proceed via a stepwise pathway featuring an electrophilic attack on the benzylic carbon of benzazetidine.
基金supported by the Ministry of Science and Technology(2016YFA0602900)the National Natural Science Foundation of China(21372224,21232008,21420102003,21521002)+1 种基金Shandong Province Independent Innovation and Achievements Transformation of Special(2014XGC06001)the Chinese Academy of Sciences
文摘A convergent construction of [2,3]-fused indoline tetrahydropyridazines via an I2/tert-butyl hydroperoxide(TBHP) catalyzed three-component dearomative oxidative coupling of indoles, hydrazines and acetophenone was established in moderate to good yields. This protocol provides a new approach for the synthesis of these biologically interesting fused indolines.
基金the Shanghai Institute of Materia Medicathe Chinese Academy of Sciences+4 种基金the National Natural Science Foundation of China(Nos.21772211 and 21920102003)the Youth Innovation Promotion Association CAS(Nos.2014229 and 2018293)the Science and Technology Commission of Shanghai Municipality(Nos.17JC1405000 and 18431907100)the Program of Shanghai Academic Research Leader(No.19XD1424600)the National Science&Technology Major Project“Key New Drug Creation and Manufacturing Program”,China(No.2018ZX09711002-006)for financial support。
文摘We report herein a palladium-catalyzed diarylative dearomatization of indole by employing thioester and arylboronic acid as the aryl electrophiles.The reaction involved a decarbonylation/migratory insertion/terminal Suzuki coupling procedure.Substrates bearing various functional groups are well tolerated in the reaction,affording the diarylated indoline skeletons in moderate to good yields.
基金supported by NSFC for Creative Research Groups(21421004) and Distinguished Young Scholars(21325625),NSFC/ChinaOriental Scholarship+4 种基金Fundamental Research Funds for the Central Universities(WJ1416005 and WJ1315025)Scientific Committee of Shanghai(14ZR1409700and 15XD1501400)Programme of Introducing Talents of Discipline to Universities(B16017)Science Foundation for the Excellent Youth Scholars of Hebei Education Department(Y2012017)Science Foundation for Oversea Scholars of Hebei(C201400324)
文摘Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region.Two indoline D-A-π-A motif sensitizers(WS-2 and WS-39) that possess similar light response area but distinctly reversed feature in photovoltaic performance are selected as the specific cosensitization couple. That is, WS-2 shows quite high photocurrent but low photovoltage, and WS-39 gives relatively low photocurrent but quite high photo voltage. Due to the obvious "barrel effect",both dyes show medium PCE around8.50%. In contrast with the previous cosensitization strategy mostly focused on the compensation of light response region, herein we perform different cosensitization sequence, for taking insight into the balance of photocurrent and photo voltage, and achieving the synergistic improvement in power conversion efficiency(PCE). Electronic impedance spectra(EIS) indicate that exploiting dye WS-39 with high V_(OC) value as the primary sensitizer can repress the charge recombination more effectively, resulting in superior V_(OC) rather than using dye WS-2 with high J_(SC)as the primary sensitizer. As a consequence, a high PCE value of 9.48% is obtained with the delicate cosensitization using WS-39 as primary dye and WS-2 as accessory dye, which is higher than the corresponding devices sensitized by each individual dye(around 8.48-8.67%). It provides an effective optimizing strategy of cosensitization how to combine the individual dye advantages for developing highly efficient solar cells.
基金the National Natural Science Foundation of China(Nos.21472172,21272212)Natural Science Foundation of Zhejiang Province(No.LY17B060009)。
文摘The copper-catalyzed directed dearomatization of indoles with the assistance of directing groups has been developed for the synthesis of 2,3-diazido indolines with good yields and excellent diastereoselectivities in aqueous solution.The resultant 2,3-diazides can be smoothly converted to other functional groups,including vicinal diamines,triazoles and benzotriazoles,in a single step.
基金supported by the National Natural Science Foundation of China (2116110444 and 21172073)National Basic Research Program of China (973 Project, 2011CB808400)+1 种基金the Fundamental Research Funds for the Central Universities (WJ0913001)Scientific Committee of Shanghai (10520709700)
文摘Functional organic dyes have promising prospect in dye-sensitized solar cells as a crucial element, of which sensitizers based on donor-π-acceptor are the most important dyes. On the basis of the structures of the aromatic amine donors such as triphenylamine and indoline, this paper reviews the photoelectric conversion properties of organic sensitizers since 2008, and highlights research work in our laboratory in this area.
基金We are grateful for financial support from the National Natural Science Foundation of China(grant no.22071187)the Natural Science Foundation of Jiangsu Province(grant no.BK20190213)+3 种基金the Shenzhen Nobel Prize Scientists Laboratory Project(grant no.C17783101)the Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002)the Natural Science Foundation of Hubei Province(grant nos.2020CFA036 and 2021CFA069)the Scientific Research Project of Education Department of Hubei Province(grant no.B2020057).We are grateful to the High Performance Computing Center and the CHEM high performance supercomputer cluster(CHEM HPC)of the Southern University of Science and Technology.
文摘Transition metal-catalyzed asymmetric hydrogenation(AH)of unprotected indoles has mainly been applied to alkyl substituted unprotected indoles.However,the challenging aryl substituted unprotected indoles with poor reactivity and enantioselectivity(≤42%ee)could not be hydrogenated well.In this work,a highly efficient Ir/bisphosphine-thiourea ligand ZhaoPhos catalytic system for the AH of challenging aryl substituted unprotected indoles has been successfully developed for the first time with high reactivity and excellent stereoselective control.Moreover,a series of 2-alkyl-substituted and 2,3-disubstituted unprotected indoles were also well tolerated in this catalytic system.A wide variety of chiral indoline derivatives were obtained in good to high yields with excellent stereoselectivities(75–99%yields,>20:1 dr,and 86–99%ee).The anion-binding activation strategy played an important role in accessing both high reactivity and excellent stereoselectivity,which was formed between the catalyst and unprotected indoles in situ-generating iminium ion with the assistance of Brønsted acid.A possible catalytic mechanism was proposed for this Ir-catalyzed AH according to density functional theory calculations and control experiment results.Readily available substrates,a broad range of substrate tolerance,an efficient chiral catalytic system,and a gram-scale protocol further demonstrated the potential practicality of this methodology.
