Homogeneous C-H and C-X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds.However,th...Homogeneous C-H and C-X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds.However,the catalysts employed in homogeneous catalysis are generally expensive,sensitive,and difficult to separate from the reaction mixture and reuse.With the rapid development of heterogeneous catalysis,heterogeneous C-H and C-X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds.This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C-H and C-X borylation strategies.We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.展开更多
In order to obtain high efficiency of organic light-emitting diodes and organic solar cells,a series of DPP-based four-coordinate organoboron compounds have been designed for photoelectric functional materials.The eff...In order to obtain high efficiency of organic light-emitting diodes and organic solar cells,a series of DPP-based four-coordinate organoboron compounds have been designed for photoelectric functional materials.The effects of electron-donating and-withdrawing substituent on the electronic and optical properties have been investigated by using density functional theory(DFT)and time-dependent DFT(TD-DFT)approaches systematically.It turned out that electron-donating and-withdrawing groups can tune effectively the frontier molecular orbital(FMO)energy level,energy gap,and absorption and fluorescence spectra.The introduction of electron-withdrawing groups for the parent molecule HBDPP(2,5-bis(diphenylboryl)-3,6-bis(pyridin-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)favors the decrease for the FMO energy(E_(LUMO)and E_(HOMO)),HOMO-LUMO gaps(E_(g)),and the downhill energetic driving force(ΔEL-L),while the electron-donating groups can increase E_(LUMO),E_(HOMO),E_(g),andΔEL-L compared with that of HBDPP,respectively.The absorption and fluorescence spectra of the electron-withdrawing substituted derivatives exhibit bathochromic shifts,while the absorption and fluorescence spectra of the electrondonating substituted derivatives show hypsochromic shifts compared with the parent molecule HBDPP,respectively.Furthermore,the stronger the electron-withdrawing/donating ability of group is,the more significant the effect in the optoelectronic properties.展开更多
Developing efficient dual-phase emission emitters upon organoboron luminophores remains a formidable challenge due to the ubiquitous self-absorption and deleterious π-π interactions from aromatic structure.Here, a n...Developing efficient dual-phase emission emitters upon organoboron luminophores remains a formidable challenge due to the ubiquitous self-absorption and deleterious π-π interactions from aromatic structure.Here, a new family of benzothiazole-enolate-based organoboron luminophores(HN1-4) with effective dual-phase emission was constructed. HN4 showed almost the highest quantum yield(QY) among this type of compound so far. The three-ring-fused rigid skeleton and moderate intramolecular charge transfer(ICT) effect ensured that HN4 could give rise to extremely strong emission in any solution(QY up to 99%). X-ray crystallographic analysis showed that the twisted core structure constructed by the boronic coordination of two penta-fluorobenzene of HN4 was responsible for intense emission in the solid state(QY up to 68%). Besides, HN4 exhibited a unique response to mechanical force accompanied by a reversible change of the QY. We believe that this strategy provides beneficial inspiration and methodology to design materials with high emissive quantum yield that can be used in a variety of luminescent events.展开更多
Novel bioengineering functional organoboron polymers were synthesized by 1) amidolysis of poly(acrcylic acid) (PAA) with 2-aminoethyldiphenyl borinate (2-AEPB), 2) esterification of organoboron PAA polymer (PAA-B) wit...Novel bioengineering functional organoboron polymers were synthesized by 1) amidolysis of poly(acrcylic acid) (PAA) with 2-aminoethyldiphenyl borinate (2-AEPB), 2) esterification of organoboron PAA polymer (PAA-B) with a-hydroxy-methoxypoly(ethylene oxide) (PEO) as a compatibilizer and 3) conjugation of organoboron PEO branches (PAA-B-PEO) with folic acid (FA) as a targeting agent. Structure and composition of the synthesized polymers were characterized by FTIR-ATR and 1H (13C) NMR spectroscopy, chemical and physical analysis methods. Anti-tumor activity of organoboron functional polymer and its complex with FA (PAA-B-PEO-F) against cancer and normal cells were evaluated by using different biochemical methods such as cytotoxicity, statistical, apoptotic and necrotic cell indexes, double staining and caspase-3 immune staining, light and fluorescence inverted microscope analyses. It was found that citotoxicity and apoptotic/necrotic effects of polymers significantly depend on the structure and composition of studied polymers, and increase the following raw: PAA << PAA-B < PAA-B-PEO < PAA-B-PEO-F. Among them, PAA-B-PEO-F complex at 400 mg mL–1 concentration as a therapeutic drug exhibits minimal toxicity toward the nor-mal cells, but influential for HeLa cancer cells.展开更多
The development of n-type polymer thermoelectrics lags far behind that of p-type ones in view of material diversity and performance.New structural insights into the thermoelectric performance are needed for efficient ...The development of n-type polymer thermoelectrics lags far behind that of p-type ones in view of material diversity and performance.New structural insights into the thermoelectric performance are needed for efficient n-type polymer thermoelectric materials.Herein,we developed three acceptor-acceptor type organoboron polymers and investigated the effect of backbone configuration on thermoelectric performance.The three polymers are designed based on double B←N bridged bipyridine(BNBP)unit with monomeric thieno[3,4-c]pyrrole-4,6-dione(TPD),TPD dimer and TPD trimer as the copolymerizing units,respectively.The three polymers show similar low LUMO energy levels but different backbone configuration.Compared with the wavy backbone configuration,the pseudo-straight backbone configuration imparts the polymer with much enhanced crystallinity and electron mobility.As a result,after n-doping,the polymer with pseudo-straight configuration shows much higher electronic conductivity and power factor.We think these findings could serve as important guidelines for molecular design toward efficient n-type polymer thermoelectric materials.展开更多
A novel method for synthesizingα-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds.As coupling partners,readily available organoboron compounds(alken...A novel method for synthesizingα-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds.As coupling partners,readily available organoboron compounds(alkenyl,allyl,and allenyl B(pin))were employed.Based on the substrates,pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process(from carbon to boron)would occur,delivering theα-oxygen organoboron compounds with great diversities.Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process.Besides,no matter which isomer of substrate(Z or E)was used,the reaction withβ-aryl-substituted alkenyl B(pin)affords both isomers of products(Z and E,separable through column chromatography).Trapping experiments indicated the triplet energy transfer process was involved.展开更多
α-Functionalized organoborons are useful building blocks and key structural elements in functional molecules.Their previous synthesis relied on the famous Matteson reaction or the late-stage borylative modification o...α-Functionalized organoborons are useful building blocks and key structural elements in functional molecules.Their previous synthesis relied on the famous Matteson reaction or the late-stage borylative modification of alkynes or alkenes.Recently,the synthetic transformation of borylated building blocks offers another useful strategy and is currently actively explored.We report herein that B(MIDA)-propargylic alcohols(BPAs) are a useful type of borylated building blocks.Bearing two complementary functional group handles(alkyne and hydroxyl) in close proximity,the redox-neutral [3,3] and [2,3] sigmatropic rearrangements of BPAs allow the efficient synthesis of several types of α-functionalized boronates,including α,β-unsaturated acylborons,α-S/P-substituted allenylborons,boryl-substituted thiazoles and a borylated α,β-unsaturated hydrazine,some of which are otherwise challenging targets using other synthetic methods.展开更多
Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are ...Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are rare.Herein,we report a highly enantioselective nickel-catalyzed alkylation reaction of aldehydes,using readily available alkylborons as nucleophiles.A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields.The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2-symmetric chiral NHC ligand.This protocol features excellent enantiocontrol,mild conditions,and good functional group compatibility.展开更多
Organoborons are commonly used building blocks for rapidly increasing molecular complexity.Although significant progress has been made in the selective functionalization of mono-organoborons,the site-selective functio...Organoborons are commonly used building blocks for rapidly increasing molecular complexity.Although significant progress has been made in the selective functionalization of mono-organoborons,the site-selective functionalization of poly(organoborons)has attracted substantial interest in organic synthesis,pharmaceuticals,and agrochemicals due to the presence of multiple potential reaction sites.This review discusses various activation modes of the target C–B bond,with diverse transformations being achieved in both a selective and efficient manner.Recent advances in the catalytic selective transformations of 1,n-diboronates through ionic and radical pathways are highlighted.Furthermore,we summarize the existing challenges and future research directions in this field.展开更多
Photoresponsive smart materials,which exhibit swift or instantaneous responses to external light stimuli,are pivotal for advancing the development of novel smart devices.Among these materials,photoresponsive tetracoor...Photoresponsive smart materials,which exhibit swift or instantaneous responses to external light stimuli,are pivotal for advancing the development of novel smart devices.Among these materials,photoresponsive tetracoordinate arylboron com-pounds emerge as prominent molecular systems,owing to their captivating photochemical mechanisms and photophysical transformations.In recent years,these molecules have experienced notable progress,leading to the emergence of numerous organic boron photoresponsive molecular systems with innovative structures and exceptional performance.In this comprehensive review,we present a thorough examination of the latest advancements in the field,systematically elucidating the design strategies and structure-activity relationships of these mol-ecules.Furthermore,we delve into the photoresponse mechanisms of various molecules and summarize their unique characteristics.Ultimately,we analyze the challenges,opportunities,and prospects encountered in this exciting field of research.展开更多
Pd-catalyzed cross-coupling reactions of chloropyrimidines with alkenylboronic acids readily proceed to give the corresponding alkenylpyrimidines in high to excellent yields. The coupling reaction of 2,4-dichloropyrim...Pd-catalyzed cross-coupling reactions of chloropyrimidines with alkenylboronic acids readily proceed to give the corresponding alkenylpyrimidines in high to excellent yields. The coupling reaction of 2,4-dichloropyrimidine or 2,4,6-trichloropyrimidine with one equivalent of alkenylboronic acid occurred more easily on 4-position than on 2-position, which implied that the reaction is highly regioselective. The reaction is stereospecific since the configu-ration of C=C remained intact. The preliminary study on the cross-coupling reactions of 2,4,6-trichlorotriazine with one equivalent of arylboronic acids showed that the reactions afforded the monosubstituted triazines in moder-ate yields. The effect of steric hindrance of the substitutents on the reactions was found.展开更多
Organoboron reagents have garnered considerable attention due to their distinct properties. In recent years, boronic acids and boronate esters have been important intermediates for cross-coupling reactions and other f...Organoboron reagents have garnered considerable attention due to their distinct properties. In recent years, boronic acids and boronate esters have been important intermediates for cross-coupling reactions and other functional group construction and are often used to synthesize small organic molecules, drugs, and bioactive substances. In this feature article, we encapsulate the strategy of harnessing the unique properties of organoboron reagents to overcome challenges encountered in conventional polymer synthesis. We delve into the synthesis of boron-containing monomers and polymer materials, unraveling the unique attributes of these newfound polymers while offering innovative insights into their application within recyclable or reprocessable materials. We develop organoboron-based photocatalysts, employing their inner-sphere electron transfer(ISET) mechanisms to initiate controlled radical polymerization. We utilize alkylborane to initiate controlled radical polymerization and further designed B-alkylcatecholboranes to prepare ultra-high molecular weight polymers. Notably, we also propose a liquid-phase synthesis method based on organoboron tags and apply it to the precise synthesis of sequence-controlled conjugated polymers.These advancements open up new frontiers in the realm of polymer science, and the versatility and potential of organoboron reagents in polymer synthesis continue to inspire exciting research endeavors.展开更多
Comprehensive Summary A family of polyaryl 2-(pyridin-2-yl)phenol-based four-coordinate organoboron complexes were prepared in good yields via deconstructive cycloaromatization of indolizines,cyclopropenones,and boric...Comprehensive Summary A family of polyaryl 2-(pyridin-2-yl)phenol-based four-coordinate organoboron complexes were prepared in good yields via deconstructive cycloaromatization of indolizines,cyclopropenones,and boric acids.The photoluminescence measurements have revealed that these N,Oπ-conjugated tetracoordinate boron complexes display bright fluorescence,large Stokes shifts,and good quantum yields(Φlum=0.15-0.45).In addition,the DFT calculations were carried out to deepen the understanding of the electronic structures and optoelectronic properties of these structurally unprecedented tetracoordinate boron complexes.展开更多
Skipped dienes are of great importance but remain challenging to synthesize because of the presence of a sp hybrid carbon between the two alkenes.Herein,we have developed the first nickel-catalyzed regio-,(E)-stereo-a...Skipped dienes are of great importance but remain challenging to synthesize because of the presence of a sp hybrid carbon between the two alkenes.Herein,we have developed the first nickel-catalyzed regio-,(E)-stereo-and linear-selective ring-opening/cross-coupling reaction of vinylaziridines with organoboronic acids under mild conditions to construct various skipped aminodienes.The reaction exhibits wide functional-group compatibility,and could be adapted for the introduction of skipped aminodiene functionality into bioactive molecules.展开更多
A new class of near-infrared(NIR)fluorescent organoboron AIEgens was successfully developed for latent fingerprints(LFPs)imaging.They exhibit real-time and in situ high-resolution imaging performance at 1-3 levels of ...A new class of near-infrared(NIR)fluorescent organoboron AIEgens was successfully developed for latent fingerprints(LFPs)imaging.They exhibit real-time and in situ high-resolution imaging performance at 1-3 levels of LFPs by spraying method.In addition,we systematically elucidate the fingerprint imaging mechanism of these AIEgens.Significantly,the excellent level 3 structural imaging capabilities enable the application of them for analyzing incomplete LFPs and identifying individuals in different scenarios.展开更多
A new family of fluoroboronated pyridylhydrazinyl aldehyde hydrozone fluorophores named BOPAHs were developed via a simple one-pot two-step reaction from chloro-2-hydrazinylpyridine and aromatic aldehyde derivatives.T...A new family of fluoroboronated pyridylhydrazinyl aldehyde hydrozone fluorophores named BOPAHs were developed via a simple one-pot two-step reaction from chloro-2-hydrazinylpyridine and aromatic aldehyde derivatives.They were well characterized by NMR,HRMS,and X-ray crystal structures.They exhibit main absorption from 400 nm to 600 nm and emission bands from 500 nm to 700 nm.The absorption/emission bands redshift with increased polarity of solvents indicate a distinct intramolecular charge transfer characteristic,further confirmed by density functional theory(DFT)calculations.These BOPAHs display weak fluorescence in solutions,but they exhibit obvious aggregation-induced emission properties,possibly resulting from weak intermolecular interactions by fixing the molecular conformations in aggregate states.展开更多
基金supported by grants from the National Natural Science Foundation of China(Nos.22271313,21602096)the Fund for Academic Innovation Teams of South-Central Minzu University(No.XTZ24015)South-Central Minzu University.
文摘Homogeneous C-H and C-X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds.However,the catalysts employed in homogeneous catalysis are generally expensive,sensitive,and difficult to separate from the reaction mixture and reuse.With the rapid development of heterogeneous catalysis,heterogeneous C-H and C-X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds.This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C-H and C-X borylation strategies.We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
基金the National Natural Science Foundation of China(21563002)the Natural Science Foundation of Inner Mongolia Autonomous Region(2021LHMS02001)the Research Program of Sciences at Universities of Inner Mongolia Autonomous Region(NJZY21175)
文摘In order to obtain high efficiency of organic light-emitting diodes and organic solar cells,a series of DPP-based four-coordinate organoboron compounds have been designed for photoelectric functional materials.The effects of electron-donating and-withdrawing substituent on the electronic and optical properties have been investigated by using density functional theory(DFT)and time-dependent DFT(TD-DFT)approaches systematically.It turned out that electron-donating and-withdrawing groups can tune effectively the frontier molecular orbital(FMO)energy level,energy gap,and absorption and fluorescence spectra.The introduction of electron-withdrawing groups for the parent molecule HBDPP(2,5-bis(diphenylboryl)-3,6-bis(pyridin-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)favors the decrease for the FMO energy(E_(LUMO)and E_(HOMO)),HOMO-LUMO gaps(E_(g)),and the downhill energetic driving force(ΔEL-L),while the electron-donating groups can increase E_(LUMO),E_(HOMO),E_(g),andΔEL-L compared with that of HBDPP,respectively.The absorption and fluorescence spectra of the electron-withdrawing substituted derivatives exhibit bathochromic shifts,while the absorption and fluorescence spectra of the electrondonating substituted derivatives show hypsochromic shifts compared with the parent molecule HBDPP,respectively.Furthermore,the stronger the electron-withdrawing/donating ability of group is,the more significant the effect in the optoelectronic properties.
基金financially supported by the National Natural Science Foundation of China(No.21975046)partially from the National Key Research and Development Program of China(No.2017YFA0207700)。
文摘Developing efficient dual-phase emission emitters upon organoboron luminophores remains a formidable challenge due to the ubiquitous self-absorption and deleterious π-π interactions from aromatic structure.Here, a new family of benzothiazole-enolate-based organoboron luminophores(HN1-4) with effective dual-phase emission was constructed. HN4 showed almost the highest quantum yield(QY) among this type of compound so far. The three-ring-fused rigid skeleton and moderate intramolecular charge transfer(ICT) effect ensured that HN4 could give rise to extremely strong emission in any solution(QY up to 99%). X-ray crystallographic analysis showed that the twisted core structure constructed by the boronic coordination of two penta-fluorobenzene of HN4 was responsible for intense emission in the solid state(QY up to 68%). Besides, HN4 exhibited a unique response to mechanical force accompanied by a reversible change of the QY. We believe that this strategy provides beneficial inspiration and methodology to design materials with high emissive quantum yield that can be used in a variety of luminescent events.
文摘Novel bioengineering functional organoboron polymers were synthesized by 1) amidolysis of poly(acrcylic acid) (PAA) with 2-aminoethyldiphenyl borinate (2-AEPB), 2) esterification of organoboron PAA polymer (PAA-B) with a-hydroxy-methoxypoly(ethylene oxide) (PEO) as a compatibilizer and 3) conjugation of organoboron PEO branches (PAA-B-PEO) with folic acid (FA) as a targeting agent. Structure and composition of the synthesized polymers were characterized by FTIR-ATR and 1H (13C) NMR spectroscopy, chemical and physical analysis methods. Anti-tumor activity of organoboron functional polymer and its complex with FA (PAA-B-PEO-F) against cancer and normal cells were evaluated by using different biochemical methods such as cytotoxicity, statistical, apoptotic and necrotic cell indexes, double staining and caspase-3 immune staining, light and fluorescence inverted microscope analyses. It was found that citotoxicity and apoptotic/necrotic effects of polymers significantly depend on the structure and composition of studied polymers, and increase the following raw: PAA << PAA-B < PAA-B-PEO < PAA-B-PEO-F. Among them, PAA-B-PEO-F complex at 400 mg mL–1 concentration as a therapeutic drug exhibits minimal toxicity toward the nor-mal cells, but influential for HeLa cancer cells.
基金the National Natural Science Foundation of China(Nos.22075271,21625403,21875244 and 21875241)B.M.thanks the financial supports by State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences and the Jilin Scientific and Technological Development Program(No.20220508142RC).
文摘The development of n-type polymer thermoelectrics lags far behind that of p-type ones in view of material diversity and performance.New structural insights into the thermoelectric performance are needed for efficient n-type polymer thermoelectric materials.Herein,we developed three acceptor-acceptor type organoboron polymers and investigated the effect of backbone configuration on thermoelectric performance.The three polymers are designed based on double B←N bridged bipyridine(BNBP)unit with monomeric thieno[3,4-c]pyrrole-4,6-dione(TPD),TPD dimer and TPD trimer as the copolymerizing units,respectively.The three polymers show similar low LUMO energy levels but different backbone configuration.Compared with the wavy backbone configuration,the pseudo-straight backbone configuration imparts the polymer with much enhanced crystallinity and electron mobility.As a result,after n-doping,the polymer with pseudo-straight configuration shows much higher electronic conductivity and power factor.We think these findings could serve as important guidelines for molecular design toward efficient n-type polymer thermoelectric materials.
基金supported by the National Natural Science Foundation of China(22101261)the Natural Science Foundation of Henan Province(232300421087,232301420045)the Zhengzhou University of China(2023ZZUJGXM168).
文摘A novel method for synthesizingα-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds.As coupling partners,readily available organoboron compounds(alkenyl,allyl,and allenyl B(pin))were employed.Based on the substrates,pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process(from carbon to boron)would occur,delivering theα-oxygen organoboron compounds with great diversities.Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process.Besides,no matter which isomer of substrate(Z or E)was used,the reaction withβ-aryl-substituted alkenyl B(pin)affords both isomers of products(Z and E,separable through column chromatography).Trapping experiments indicated the triplet energy transfer process was involved.
基金supported by the National Natural Science Foundation of China (22022114,21971261)the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Y093)Guangdong Basic Research Center of Excellence for Functional Molecular Engineering。
文摘α-Functionalized organoborons are useful building blocks and key structural elements in functional molecules.Their previous synthesis relied on the famous Matteson reaction or the late-stage borylative modification of alkynes or alkenes.Recently,the synthetic transformation of borylated building blocks offers another useful strategy and is currently actively explored.We report herein that B(MIDA)-propargylic alcohols(BPAs) are a useful type of borylated building blocks.Bearing two complementary functional group handles(alkyne and hydroxyl) in close proximity,the redox-neutral [3,3] and [2,3] sigmatropic rearrangements of BPAs allow the efficient synthesis of several types of α-functionalized boronates,including α,β-unsaturated acylborons,α-S/P-substituted allenylborons,boryl-substituted thiazoles and a borylated α,β-unsaturated hydrazine,some of which are otherwise challenging targets using other synthetic methods.
基金supported by the National Key R&D Program of China(2022YFA1503702,2021YFF0701600)the National Natural Science Foundation of China(22325110,92256303,21821002,22171280)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000)the Program of Shanghai Academic Research Leader(22XD1424900)the CAS Youth Interdisciplinary Team(JCTD-2021-11)and the Ningbo Natural Science Foundation(2022J017).
文摘Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are rare.Herein,we report a highly enantioselective nickel-catalyzed alkylation reaction of aldehydes,using readily available alkylborons as nucleophiles.A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields.The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2-symmetric chiral NHC ligand.This protocol features excellent enantiocontrol,mild conditions,and good functional group compatibility.
基金We gratefully acknowledge NSFC(Grant No.22101177)the Science and Technology Commission of Shanghai Municipality(Grant Nos.23YF1426700 and 21ZR1442000)start-up funding of ShanghaiTech University for their generous financial support.
文摘Organoborons are commonly used building blocks for rapidly increasing molecular complexity.Although significant progress has been made in the selective functionalization of mono-organoborons,the site-selective functionalization of poly(organoborons)has attracted substantial interest in organic synthesis,pharmaceuticals,and agrochemicals due to the presence of multiple potential reaction sites.This review discusses various activation modes of the target C–B bond,with diverse transformations being achieved in both a selective and efficient manner.Recent advances in the catalytic selective transformations of 1,n-diboronates through ionic and radical pathways are highlighted.Furthermore,we summarize the existing challenges and future research directions in this field.
基金supported by the Topnotch Talents Program of Henan Agricultural University(30501032,30500418,30501049)the National Natural Science Foundation of China(22305070,U20041101)+2 种基金the Natural Science Foundation of Henan Province(232300420132)the Scientific and Technological Project of the Henan Province(222102240043)the Distinguished Young Scholar Fund Project of Hunan Province Natural Science Foundation(2023JЛ10041)。
文摘Photoresponsive smart materials,which exhibit swift or instantaneous responses to external light stimuli,are pivotal for advancing the development of novel smart devices.Among these materials,photoresponsive tetracoordinate arylboron com-pounds emerge as prominent molecular systems,owing to their captivating photochemical mechanisms and photophysical transformations.In recent years,these molecules have experienced notable progress,leading to the emergence of numerous organic boron photoresponsive molecular systems with innovative structures and exceptional performance.In this comprehensive review,we present a thorough examination of the latest advancements in the field,systematically elucidating the design strategies and structure-activity relationships of these mol-ecules.Furthermore,we delve into the photoresponse mechanisms of various molecules and summarize their unique characteristics.Ultimately,we analyze the challenges,opportunities,and prospects encountered in this exciting field of research.
基金the National Natural Science Foundation of China (No. 20272073).
文摘Pd-catalyzed cross-coupling reactions of chloropyrimidines with alkenylboronic acids readily proceed to give the corresponding alkenylpyrimidines in high to excellent yields. The coupling reaction of 2,4-dichloropyrimidine or 2,4,6-trichloropyrimidine with one equivalent of alkenylboronic acid occurred more easily on 4-position than on 2-position, which implied that the reaction is highly regioselective. The reaction is stereospecific since the configu-ration of C=C remained intact. The preliminary study on the cross-coupling reactions of 2,4,6-trichlorotriazine with one equivalent of arylboronic acids showed that the reactions afforded the monosubstituted triazines in moder-ate yields. The effect of steric hindrance of the substitutents on the reactions was found.
基金supported by the National Natural Science Foundation of China (22271057, 22201045)the Natural Science Foundation of Shanghai (22ZR1406000)the State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science, and Fudan University。
文摘Organoboron reagents have garnered considerable attention due to their distinct properties. In recent years, boronic acids and boronate esters have been important intermediates for cross-coupling reactions and other functional group construction and are often used to synthesize small organic molecules, drugs, and bioactive substances. In this feature article, we encapsulate the strategy of harnessing the unique properties of organoboron reagents to overcome challenges encountered in conventional polymer synthesis. We delve into the synthesis of boron-containing monomers and polymer materials, unraveling the unique attributes of these newfound polymers while offering innovative insights into their application within recyclable or reprocessable materials. We develop organoboron-based photocatalysts, employing their inner-sphere electron transfer(ISET) mechanisms to initiate controlled radical polymerization. We utilize alkylborane to initiate controlled radical polymerization and further designed B-alkylcatecholboranes to prepare ultra-high molecular weight polymers. Notably, we also propose a liquid-phase synthesis method based on organoboron tags and apply it to the precise synthesis of sequence-controlled conjugated polymers.These advancements open up new frontiers in the realm of polymer science, and the versatility and potential of organoboron reagents in polymer synthesis continue to inspire exciting research endeavors.
基金supported by the Science and Technology Innovation Project of Guangdong Drug Administration(2021TDB36,2021ZDB14)Special Fund for Scientific and Technological Innovation Strategy of Guangdong Province(pdjh2023b0281).
文摘Comprehensive Summary A family of polyaryl 2-(pyridin-2-yl)phenol-based four-coordinate organoboron complexes were prepared in good yields via deconstructive cycloaromatization of indolizines,cyclopropenones,and boric acids.The photoluminescence measurements have revealed that these N,Oπ-conjugated tetracoordinate boron complexes display bright fluorescence,large Stokes shifts,and good quantum yields(Φlum=0.15-0.45).In addition,the DFT calculations were carried out to deepen the understanding of the electronic structures and optoelectronic properties of these structurally unprecedented tetracoordinate boron complexes.
基金the funding support of this work by the National Natural Science Foundation of China(Nos.21831005 and 21991112)National Key R&D Program of China(No.2018YFE0126800).
文摘Skipped dienes are of great importance but remain challenging to synthesize because of the presence of a sp hybrid carbon between the two alkenes.Herein,we have developed the first nickel-catalyzed regio-,(E)-stereo-and linear-selective ring-opening/cross-coupling reaction of vinylaziridines with organoboronic acids under mild conditions to construct various skipped aminodienes.The reaction exhibits wide functional-group compatibility,and could be adapted for the introduction of skipped aminodiene functionality into bioactive molecules.
基金supported by the Topnotch Talents Program of Henan Agricultural University(30501032)the National Natural Science Foundation of China(52003228 and 52273197)+2 种基金the Science,Technology and Innovation Commission of Shenzhen Municipality(JCYJ2021324134613038)the Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001)Shenzhen Peacock Team Project(KQTD20210811090142053).
文摘A new class of near-infrared(NIR)fluorescent organoboron AIEgens was successfully developed for latent fingerprints(LFPs)imaging.They exhibit real-time and in situ high-resolution imaging performance at 1-3 levels of LFPs by spraying method.In addition,we systematically elucidate the fingerprint imaging mechanism of these AIEgens.Significantly,the excellent level 3 structural imaging capabilities enable the application of them for analyzing incomplete LFPs and identifying individuals in different scenarios.
文摘A new family of fluoroboronated pyridylhydrazinyl aldehyde hydrozone fluorophores named BOPAHs were developed via a simple one-pot two-step reaction from chloro-2-hydrazinylpyridine and aromatic aldehyde derivatives.They were well characterized by NMR,HRMS,and X-ray crystal structures.They exhibit main absorption from 400 nm to 600 nm and emission bands from 500 nm to 700 nm.The absorption/emission bands redshift with increased polarity of solvents indicate a distinct intramolecular charge transfer characteristic,further confirmed by density functional theory(DFT)calculations.These BOPAHs display weak fluorescence in solutions,but they exhibit obvious aggregation-induced emission properties,possibly resulting from weak intermolecular interactions by fixing the molecular conformations in aggregate states.
