饱和的碳氢键氧化是合成化学和化学工业中一类重要的化学反应.然而,饱和C(sp^(3))−H键离解能(BDEs)较高、极性较弱,导致了底物难以活化和催化转化效率较低等问题.在过去的几十年,C(sp^(3))−H键的定向活化转化取得了重要的进展.其中,关于...饱和的碳氢键氧化是合成化学和化学工业中一类重要的化学反应.然而,饱和C(sp^(3))−H键离解能(BDEs)较高、极性较弱,导致了底物难以活化和催化转化效率较低等问题.在过去的几十年,C(sp^(3))−H键的定向活化转化取得了重要的进展.其中,关于C(sp^(3))−H键催化氧化的研究主要涉及一些键能低的、预活化的C−H键,包括苄基型、亚甲基型、脂肪族X−CH_(2)(X=O,N)和甲苯等,含有未活化C(sp^(3))−H键的复杂化合物的选择性氧化仍具有挑战性.例如,芳基醚C(sp^(3))−H键功能化通常采用计量的过氧化物氧化剂,或者通过单电子氧化和碱促进的去质子化进一步构建C−C/C−N键,产物选择性较低,也带来了一些不利的环境影响.因此,有必要开发高效、温和的芳基醚C(sp^(3))−H键选择氧化方法,并将其应用于有机合成和药物开发.近年来,光催化C(sp^(3))−H键氧化因其操作简便、氧化还原中性等优点,已发展成为一种有用且多样的催化研究工具.本文发展了一种利用氧气作为氧化剂,在可见光驱动下选择性地将芳基醚C(sp^(3))−H键氧化成为甲酸苯酯类产物的新方法.使用Mes-10-phenyl-Acr^(+)−BF_(4)^(-)光催化剂,高效活化多种氯源(如盐酸、无机氯盐和有机氯化物)得到氯自由基,由于其具有较高的氧化能力(+2.03 V vs.SCE)和对氢原子的亲和力,能够通过氢原子转移过程活化芳基醚C(sp^(3))−键,攫取氢自由基得到相应的烷基碳自由基(•CH_(2)OPh)中间体,进一步被分子氧选择氧化得到酯类目标产物.研究结果表明,多种链状芳基醚和不同取代(如给电子基和吸电子基)芳基醚均可发生氧化反应,高收率地合成了一系列官能团丰富的甲酸苯酯类化合物.本文方法具有反应条件温和、操作简单、官能团耐受性好以及可规模化放大等优点,并且少量的水对反应没有明显影响.机理实验研究结果表明,芳基醚C(sp^(3))−H键的断裂是反应过程的决速步骤.紫外可见吸收光谱结果表明,氯离子与催化剂之间的相互作用强于底物,并且自由基捕获实验证实反应体系中存在氯自由基和烷基碳自由基物种,表明反应经历自由基路径.此外,电子顺磁共振测试结果表明,反应过程中存在单线态氧物种,可能是激发态的光催化剂直接与氧气发生能量转移得到;同位素实验(18O)揭示了甲酸苯酯类化合物氧的来源.综上,本文实现了温和条件下光催化芳基醚C(sp^(3))−H键选择氧化反应,高收率合成了一系列甲酸苯酯类化合物.该方法避免了化学计量的过氧化物和碱等添加剂的使用以及底物的过度氧化,阐明了催化反应机制,为其他醚类化合物的C(sp^(3))−H键氧化功能化提供了新思路,为后续化学合成和药物开发提供了参考和启示.展开更多
An acetic acid-promoted C(sp^(3))-H functionalization of 2-methyl quinoline,enaminoesters and elemental sulfur for the synthesis of 3,4,5-trisubstituted isothiazoles under metal-free conditions has been developed.This...An acetic acid-promoted C(sp^(3))-H functionalization of 2-methyl quinoline,enaminoesters and elemental sulfur for the synthesis of 3,4,5-trisubstituted isothiazoles under metal-free conditions has been developed.This approach provides viable access to various 5-(quinolin-2-yl)isothiazoles in moderate to good yields with good functional group tolerance.Moreover,the success of the gram-scale reaction gives this reaction a great potential application.展开更多
Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of...Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.展开更多
A metal-free,green,and sustainable functionalization of unactivated alkyl sp^(3) C—H bonds is reported using iodine(III)as a feasible dehydrogenation agent under visible light or KBr,and alkyl chlorides,bromides,alco...A metal-free,green,and sustainable functionalization of unactivated alkyl sp^(3) C—H bonds is reported using iodine(III)as a feasible dehydrogenation agent under visible light or KBr,and alkyl chlorides,bromides,alcohols,and ketones could be constructed by addition of different coupling reagents.Cheap and safe iodobenzene diacetate was used to form a radical to activate the alkyl sp^(3) C—H bond in a highly efficient manner,which can construct different alkylation products by adding corresponding coupling reagents.展开更多
Hydrogen atom transfer(HAT)is an elementary mechanistic step in organic synthesis.The photoredox-catalyzed HAT has transformed organic synthesis by enabling the activation and subsequent cross-coupling of traditionall...Hydrogen atom transfer(HAT)is an elementary mechanistic step in organic synthesis.The photoredox-catalyzed HAT has transformed organic synthesis by enabling the activation and subsequent cross-coupling of traditionally inert yet ubiquitous C(sp^(3))-H bonds.展开更多
A copper-catalyzed decarboxylative oxidative coupling of α,β-unsaturated carboxylic acids with non-cyclic ethers is developed.This method provides a new approach for C(sp^3)–H bond functionalization of non-cyclic e...A copper-catalyzed decarboxylative oxidative coupling of α,β-unsaturated carboxylic acids with non-cyclic ethers is developed.This method provides a new approach for C(sp^3)–H bond functionalization of non-cyclic ethers. Mechanism study shows the reaction involves a radical process.展开更多
Metal-free direct α-C(sp^(3))-H intramolecular cyclization of 2-alkylthiobenzoic acid in the presence of Selectfluor is described.This novel strategy provides a facile and efficient method to access important 1,3-ben...Metal-free direct α-C(sp^(3))-H intramolecular cyclization of 2-alkylthiobenzoic acid in the presence of Selectfluor is described.This novel strategy provides a facile and efficient method to access important 1,3-benzooxathiin-4-one derivatives with good functional groups tolerance and yields.展开更多
Direct functionalization of inert C(sp^(3))–H bonds is a topic of immense contemporary interest and exceptional value in organic synthesis.The recent research has established a novel and practical protocol which feat...Direct functionalization of inert C(sp^(3))–H bonds is a topic of immense contemporary interest and exceptional value in organic synthesis.The recent research has established a novel and practical protocol which features the engagement of vinyl cation species to functionalize C(sp^(3))–H bonds.The discussion of the topic is arranged by the strategies to generate the reactive intermediates,including ionization of vinyl triflates,addition of electrophiles to alkynes,tandem cyclization of enynes or diynes,and decomposition ofβ-hydroxy-α-diazo ketones.This review closes with a personal perspective on the dynamic research area of unactivated C(sp^(3))–H functionalization via vinyl cations.Hopefully,it will provide timely illumination and beneficial guidance for organic chemists who are interested in this area.Meanwhile continued development of the field is strongly anticipated in the future.展开更多
Aliphatic alcohols and amides are highly valued,ubiquitous chemicals in synthetic chemistry.Radical-promoted regioselective functionalization of unactivated C(sp^(3))–H bonds offers an atom and step economic manner f...Aliphatic alcohols and amides are highly valued,ubiquitous chemicals in synthetic chemistry.Radical-promoted regioselective functionalization of unactivated C(sp^(3))–H bonds offers an atom and step economic manner for direct transformation of aliphatic alcohols and amides,especially structural elaboration of complex natural products and bioactive molecules without de novo synthesis.Despite the rapid growth of hydrogen atom transfer(HAT)processes mediated by O-or N-centered radicals generated from prefunctionalized precursors of alcohols and amides in the past few years,exploration of remote C(sp^(3))–H functionalization via HAT mediated by unprotected alcohols or amides lags behind,due to the difficult homolysis of O–H and N–H bonds with high bond-dissociation energies(BDEs).In this minireview,the recent advances in regioselective C(sp^(3))–H functionalization mediated by unprotected alcohols and amides are summarized.展开更多
A method of C(sp^3)-H bond functionalization of methyl azaarenes catalyzed by alumina-supported heteropoly acid and addition to isatins was developed. This transformation could be used for the synthesis of biologica...A method of C(sp^3)-H bond functionalization of methyl azaarenes catalyzed by alumina-supported heteropoly acid and addition to isatins was developed. This transformation could be used for the synthesis of biologically important 3-hydroxy-2-oxindole derivatives in good to excellent yields and the catalyst could be reused for six times without significant decrease in activity.展开更多
Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique singleelectron transfer processes,so as to achieve challenging C(sp^(3))-H...Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique singleelectron transfer processes,so as to achieve challenging C(sp^(3))-H functionalization under mild conditions.However,the specific reaction mechanism and relevant electron transfer process still need to be clarified.Here,a highly regioselective Ir^(Ⅲ)/Ni^(Ⅱ)-metallaphotoredox-catalyzed hydroalkylation of asymmetrical internal alkyne with an etherα-hetero C(sp^(3))-H bond has been investigated by density functional theory(DFT)calculations.A novel radical mechanism was predicted to merge oxidative quenching(Ir^(Ⅲ)-*Ir^(Ⅲ)-Ir^(Ⅳ)-Ir^(Ⅲ))and nickel catalytic cycles(NiⅡ-NiⅢ-NiI-NiⅢ-NiⅡ)for this C(sp^(3))-H functionalization to construct C(sp^(3))-C(sp^(2))bonds.It consists of seven major steps:the single-electron transfer involved in the photoredox cycle for generating active Ni(Ⅰ)-chloride complexes,proton-coupled electron transfer process to provide α-carbon-centered tetrahydrofuran(THF)radicals,radical capture by Ni(Ⅱ),reductive elimination to obtain 2-chlorotetrahydrofuran,alkyne oxidative hydrometallation,innersphere electron transfer,and σ-bond metathesis to yield the desired alkyne hydroalkylation product.Importantly,both the thermodynamic performance for redox potentials and the kinetic exploration for energy barriers and electron-transfer rates have also been evaluated for the corresponding electron transfer processes.In addition,the steric effects play a major role in determining the regioselectivity of alkyne oxidative hydrometallation.展开更多
Thioether skeletons are widely present in drugs,natural products,functional materials,and life science.In the past decade,the selective C–H functionalization of thioethers has been extensively studied to construct no...Thioether skeletons are widely present in drugs,natural products,functional materials,and life science.In the past decade,the selective C–H functionalization of thioethers has been extensively studied to construct novel thioether derivatives.This mini-review systematically introduces the recent advances in the field of the directα-C(sp^(3))-H functionalization of thioethers.展开更多
A conceptually novel,trifunctional sulfoximine-mediatedγ-functionalization of unactivated C(sp^(3))–H bonds has been achieved.The reaction is initiated by the photo-induced homolytic cleavage of an N–S bond in the ...A conceptually novel,trifunctional sulfoximine-mediatedγ-functionalization of unactivated C(sp^(3))–H bonds has been achieved.The reaction is initiated by the photo-induced homolytic cleavage of an N–S bond in the absence of photosensitizer,and proceeds sequentially through a cascade of 1,5-hydrogen atom transfer,1,4-functional group migration,desulfoximination and a Minisci reaction.A major feature of this approach is the use of sulfoximine as a traceless directing group.Other positive properties include mild conditions,simple operation,exclusive site-selectivity,high product diversity and the avoidance of additional photosensitizers.The protocol provides a new reaction mode for HAT-induced C(sp^(3))–H functionalization,and allows a much broader chemical space for sulfoximine studies.展开更多
文摘饱和的碳氢键氧化是合成化学和化学工业中一类重要的化学反应.然而,饱和C(sp^(3))−H键离解能(BDEs)较高、极性较弱,导致了底物难以活化和催化转化效率较低等问题.在过去的几十年,C(sp^(3))−H键的定向活化转化取得了重要的进展.其中,关于C(sp^(3))−H键催化氧化的研究主要涉及一些键能低的、预活化的C−H键,包括苄基型、亚甲基型、脂肪族X−CH_(2)(X=O,N)和甲苯等,含有未活化C(sp^(3))−H键的复杂化合物的选择性氧化仍具有挑战性.例如,芳基醚C(sp^(3))−H键功能化通常采用计量的过氧化物氧化剂,或者通过单电子氧化和碱促进的去质子化进一步构建C−C/C−N键,产物选择性较低,也带来了一些不利的环境影响.因此,有必要开发高效、温和的芳基醚C(sp^(3))−H键选择氧化方法,并将其应用于有机合成和药物开发.近年来,光催化C(sp^(3))−H键氧化因其操作简便、氧化还原中性等优点,已发展成为一种有用且多样的催化研究工具.本文发展了一种利用氧气作为氧化剂,在可见光驱动下选择性地将芳基醚C(sp^(3))−H键氧化成为甲酸苯酯类产物的新方法.使用Mes-10-phenyl-Acr^(+)−BF_(4)^(-)光催化剂,高效活化多种氯源(如盐酸、无机氯盐和有机氯化物)得到氯自由基,由于其具有较高的氧化能力(+2.03 V vs.SCE)和对氢原子的亲和力,能够通过氢原子转移过程活化芳基醚C(sp^(3))−键,攫取氢自由基得到相应的烷基碳自由基(•CH_(2)OPh)中间体,进一步被分子氧选择氧化得到酯类目标产物.研究结果表明,多种链状芳基醚和不同取代(如给电子基和吸电子基)芳基醚均可发生氧化反应,高收率地合成了一系列官能团丰富的甲酸苯酯类化合物.本文方法具有反应条件温和、操作简单、官能团耐受性好以及可规模化放大等优点,并且少量的水对反应没有明显影响.机理实验研究结果表明,芳基醚C(sp^(3))−H键的断裂是反应过程的决速步骤.紫外可见吸收光谱结果表明,氯离子与催化剂之间的相互作用强于底物,并且自由基捕获实验证实反应体系中存在氯自由基和烷基碳自由基物种,表明反应经历自由基路径.此外,电子顺磁共振测试结果表明,反应过程中存在单线态氧物种,可能是激发态的光催化剂直接与氧气发生能量转移得到;同位素实验(18O)揭示了甲酸苯酯类化合物氧的来源.综上,本文实现了温和条件下光催化芳基醚C(sp^(3))−H键选择氧化反应,高收率合成了一系列甲酸苯酯类化合物.该方法避免了化学计量的过氧化物和碱等添加剂的使用以及底物的过度氧化,阐明了催化反应机制,为其他醚类化合物的C(sp^(3))−H键氧化功能化提供了新思路,为后续化学合成和药物开发提供了参考和启示.
基金Support by the National Natural Science Foundation of China(Nos.22271244,21871226 and 21572194)Postgraduate Scientific Research Innovation Project of Hunan Province(No.CX20200631)the Open Research Fund of the School of Chemistry and Chemical Engineering of Henan Normal University(No.2022C02)is gratefully acknowledged.
文摘An acetic acid-promoted C(sp^(3))-H functionalization of 2-methyl quinoline,enaminoesters and elemental sulfur for the synthesis of 3,4,5-trisubstituted isothiazoles under metal-free conditions has been developed.This approach provides viable access to various 5-(quinolin-2-yl)isothiazoles in moderate to good yields with good functional group tolerance.Moreover,the success of the gram-scale reaction gives this reaction a great potential application.
基金the National Natural Science Foundation of China(Nos.22025206,21991094)supported by the Ministry of ScienceTechnology of the People’s Republic of China(No.2018YFE0118100)+1 种基金the CAS-NSTDA Joint Research Project(No.GJHZ2075)Dalian Science and Technology Innovation Fund(No.2019J11CY009).
文摘Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.
基金supported the Natural Science Foundation of Higher Education Institutions in Anhui Province(2022AH030133,2022AH051340)National Natural Science Foundation of China(22231003,22271008)+6 种基金Shenzhen Science and Technology Program(Grant No.KQTD20190929174023858)Shenzhen Science and Technology Innovation Committee(GXWD20201231165807007-20200812100115001)Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions(2023SHIBS0004)Horizontal Cooperation Project of Fuyang Municipal Government(SXHZ202201)Key Projects of the Support Program for Outstanding Young Talents in Anhui Province Colleges and Universities(gxyqZD2020030)Yifan Pharmaceutical Co.,Ltd.(HX2019033)Innovative Drug Design&Development Collaborative Team(TDYY2021009).
文摘A metal-free,green,and sustainable functionalization of unactivated alkyl sp^(3) C—H bonds is reported using iodine(III)as a feasible dehydrogenation agent under visible light or KBr,and alkyl chlorides,bromides,alcohols,and ketones could be constructed by addition of different coupling reagents.Cheap and safe iodobenzene diacetate was used to form a radical to activate the alkyl sp^(3) C—H bond in a highly efficient manner,which can construct different alkylation products by adding corresponding coupling reagents.
基金We are grateful for financial support from the National Key R&D Program of China(2021YFA1502500)National Natural Science Foundation of China(22071203)Fundamental Research Funds for the Central Universities(20720210014).
文摘Hydrogen atom transfer(HAT)is an elementary mechanistic step in organic synthesis.The photoredox-catalyzed HAT has transformed organic synthesis by enabling the activation and subsequent cross-coupling of traditionally inert yet ubiquitous C(sp^(3))-H bonds.
基金supported by the National Natural Science Foundation of China (21572240)
文摘A copper-catalyzed decarboxylative oxidative coupling of α,β-unsaturated carboxylic acids with non-cyclic ethers is developed.This method provides a new approach for C(sp^3)–H bond functionalization of non-cyclic ethers. Mechanism study shows the reaction involves a radical process.
基金the financial support from the National Natural Science Foundation of China(Nos.21572026,21702019)Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Changzhou University。
文摘Metal-free direct α-C(sp^(3))-H intramolecular cyclization of 2-alkylthiobenzoic acid in the presence of Selectfluor is described.This novel strategy provides a facile and efficient method to access important 1,3-benzooxathiin-4-one derivatives with good functional groups tolerance and yields.
基金supported by the National Natural Science Foundation of China(21772161,21828102)the Natural Science Foundation of Fujian Province(2019J02001)+3 种基金the President Research Funds from Xiamen University(20720180036)NFFTBS(J1310024)the Foundation of Wenzhou Science&Technology Bureau(ZY2020027)the Science&Technology Co-operation Program of Xiamen(3502Z20183015)。
文摘Direct functionalization of inert C(sp^(3))–H bonds is a topic of immense contemporary interest and exceptional value in organic synthesis.The recent research has established a novel and practical protocol which features the engagement of vinyl cation species to functionalize C(sp^(3))–H bonds.The discussion of the topic is arranged by the strategies to generate the reactive intermediates,including ionization of vinyl triflates,addition of electrophiles to alkynes,tandem cyclization of enynes or diynes,and decomposition ofβ-hydroxy-α-diazo ketones.This review closes with a personal perspective on the dynamic research area of unactivated C(sp^(3))–H functionalization via vinyl cations.Hopefully,it will provide timely illumination and beneficial guidance for organic chemists who are interested in this area.Meanwhile continued development of the field is strongly anticipated in the future.
基金C.Z.is grateful for the financial support from the National Natural Science Foundation of China(21722205 and 21971173)the Project of Scientific and Technologic Infrastructure of Suzhou(SZS201905)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Aliphatic alcohols and amides are highly valued,ubiquitous chemicals in synthetic chemistry.Radical-promoted regioselective functionalization of unactivated C(sp^(3))–H bonds offers an atom and step economic manner for direct transformation of aliphatic alcohols and amides,especially structural elaboration of complex natural products and bioactive molecules without de novo synthesis.Despite the rapid growth of hydrogen atom transfer(HAT)processes mediated by O-or N-centered radicals generated from prefunctionalized precursors of alcohols and amides in the past few years,exploration of remote C(sp^(3))–H functionalization via HAT mediated by unprotected alcohols or amides lags behind,due to the difficult homolysis of O–H and N–H bonds with high bond-dissociation energies(BDEs).In this minireview,the recent advances in regioselective C(sp^(3))–H functionalization mediated by unprotected alcohols and amides are summarized.
基金Financial support from the National Natural Science Foundation of China(No.21402103)the research fund of Qingdao Agricultural University's High-level Person(No.631303)the Scientific Research Foundation of Shandong Province Outstanding Young Scientist Award(No.BS2013YY024) were gratefully acknowledged
文摘A method of C(sp^3)-H bond functionalization of methyl azaarenes catalyzed by alumina-supported heteropoly acid and addition to isatins was developed. This transformation could be used for the synthesis of biologically important 3-hydroxy-2-oxindole derivatives in good to excellent yields and the catalyst could be reused for six times without significant decrease in activity.
文摘Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique singleelectron transfer processes,so as to achieve challenging C(sp^(3))-H functionalization under mild conditions.However,the specific reaction mechanism and relevant electron transfer process still need to be clarified.Here,a highly regioselective Ir^(Ⅲ)/Ni^(Ⅱ)-metallaphotoredox-catalyzed hydroalkylation of asymmetrical internal alkyne with an etherα-hetero C(sp^(3))-H bond has been investigated by density functional theory(DFT)calculations.A novel radical mechanism was predicted to merge oxidative quenching(Ir^(Ⅲ)-*Ir^(Ⅲ)-Ir^(Ⅳ)-Ir^(Ⅲ))and nickel catalytic cycles(NiⅡ-NiⅢ-NiI-NiⅢ-NiⅡ)for this C(sp^(3))-H functionalization to construct C(sp^(3))-C(sp^(2))bonds.It consists of seven major steps:the single-electron transfer involved in the photoredox cycle for generating active Ni(Ⅰ)-chloride complexes,proton-coupled electron transfer process to provide α-carbon-centered tetrahydrofuran(THF)radicals,radical capture by Ni(Ⅱ),reductive elimination to obtain 2-chlorotetrahydrofuran,alkyne oxidative hydrometallation,innersphere electron transfer,and σ-bond metathesis to yield the desired alkyne hydroalkylation product.Importantly,both the thermodynamic performance for redox potentials and the kinetic exploration for energy barriers and electron-transfer rates have also been evaluated for the corresponding electron transfer processes.In addition,the steric effects play a major role in determining the regioselectivity of alkyne oxidative hydrometallation.
基金support from the National Natural Science Foundation of China(NSFC,No.21702019)and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Changzhou UniversityHaibo Ge,Mazen Elsaid and Chong Liu acknowledge NSF(No.CHE-2029932),Robert A.Welch Foundation(No.D-2034-20200401),and the Texas Tech University for financial support.
文摘Thioether skeletons are widely present in drugs,natural products,functional materials,and life science.In the past decade,the selective C–H functionalization of thioethers has been extensively studied to construct novel thioether derivatives.This mini-review systematically introduces the recent advances in the field of the directα-C(sp^(3))-H functionalization of thioethers.
基金supported by the National Natural Science Foundation of China(21971173,22001185,22171201)the Natural Science Foundation of Jiangsu Province(BK20200852)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘A conceptually novel,trifunctional sulfoximine-mediatedγ-functionalization of unactivated C(sp^(3))–H bonds has been achieved.The reaction is initiated by the photo-induced homolytic cleavage of an N–S bond in the absence of photosensitizer,and proceeds sequentially through a cascade of 1,5-hydrogen atom transfer,1,4-functional group migration,desulfoximination and a Minisci reaction.A major feature of this approach is the use of sulfoximine as a traceless directing group.Other positive properties include mild conditions,simple operation,exclusive site-selectivity,high product diversity and the avoidance of additional photosensitizers.The protocol provides a new reaction mode for HAT-induced C(sp^(3))–H functionalization,and allows a much broader chemical space for sulfoximine studies.