Metal/nucleophilic Lewis base dual catalysis has been recognized as a reliable and promising strategy for finishing ideal organic synthesis over the past decades.The new strategy can usually achieve some chemical reac...Metal/nucleophilic Lewis base dual catalysis has been recognized as a reliable and promising strategy for finishing ideal organic synthesis over the past decades.The new strategy can usually achieve some chemical reactions that cannot be realized by the traditionally mono-catalytic system,dramatically expanding the synthetic utility of chemical transformations by leveraging additional activation modes.Thus considerable progress has been made in the synthesis of a wide range of heterocyclic and biologically active compounds by using the combination of diversely metal/nucleophilic Lewis base dual catalysts,including metal/phosphine,metal/N-heterocyclic carbene(NHC)and metal/tertiary amine dual catalysis systems.In this review,we describe a comprehensive and updated advance of metal/nucleophilic Lewis base dual catalytic annualtion reactions,meanwhile,the related mechanism and the application of these annulation strategies in natural product total synthesis will be highlighted in detail.展开更多
Transition metal catalysis is one of the most important tools to construct carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. Visible-light photoredox catalysis has recently drawn considerable atte...Transition metal catalysis is one of the most important tools to construct carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. Visible-light photoredox catalysis has recently drawn considerable attention of the scientific community owing to its unique activation modes and significance for the green synthesis. The merger of photoredox catalysis with transition metal catalysts, termed metallaphotoredox catalysis, has become a popular strategy for expanding the synthetic utility of visiblelight photocatalysis. This strategy has led to the discovery of novel asymmetric transformations, which are unfeasible or not easily accessible by a single catalytic system. This contemporary area of organic chemistry holds promise for the development of economical and environmentally friendly methods for the asymmetric synthesis of chiral compounds. In this review, the advances in the enantioselective metallaphotoredox catalysis(EMPC) are summarized.展开更多
Herein,we reported the stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis and found a suitable system to resolve many challenges,such as the tolerance towards the density of functional groups,th...Herein,we reported the stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis and found a suitable system to resolve many challenges,such as the tolerance towards the density of functional groups,the variability of the anomeric position,the compatibility of appropriate catalyst combinations,the regioselectivity of nucleophiles,and the match/mismatch problems between chiral substrates and chiral ligand-metal complexes.The method enables the efficient preparation of a series of unnatural C-glycosamino acid skeletons bearing two contiguous stereogenic centers in good yields with excellent diastereoselectivity.From this crucial precursor,various C-glycosamino acid derivatives have been achieved diversely.The readily prepared C-glycosamino acid hybrids will meet the growing demands for the development of new molecular entities for discovering new drugs and materials.This stereodivergent synthesis of C-glycosamino acids will further accelerate the study of their structural features,mode of action,and potential biological applications in the near future.展开更多
A new dual plldium/scandium catalysis starting fromβ-alkynyl ketones and o alkynyl anilines is reported for the first time,leading to the atom-economic synthesis of rotationally hindered C3-naphthylated indoles in mo...A new dual plldium/scandium catalysis starting fromβ-alkynyl ketones and o alkynyl anilines is reported for the first time,leading to the atom-economic synthesis of rotationally hindered C3-naphthylated indoles in moderate to good yields and high regioselectivi-ty.This method can tolerate normal air conditions,and features the use of palladium/scandium cooperative catalysts without any ligand,facile double annulation involving various internal alkynes,and good functional group tolerance.展开更多
A new process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high catalytic promoting effect on the synthesis o...A new process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high catalytic promoting effect on the synthesis of methanol from CO hydrogenation. At 443 K and 5 MPa, the synthesis of methanol could process high effectively, resulting from the synergic catalysis of Cu/ZnO solid catalyst and 2-alcohol solvent catalyst. The primary results showed that when 2-butanol was used as reaction solvent, the one-pass average yield and the selectivity of methanol, in 40 h continuous reaction at temperature as low as 443 K and 5 MPa, were high up to 46.51% and 98.94% respectively. The catalytic activity was stable and the reaction temperature was 80 K or so lower than that in current industry synthesis process. This new process hopefully will become a practical method for methanol synthesis at low temperature.展开更多
制备了气相催化氧化2-甲基吡啶合成2-吡啶甲醛的双金属Bi-Mo/TiO_2催化剂,采用XRD、H_2-TPR、SEM和XPS对催化剂进行了表征,并考察了催化剂组成、反应温度、原料流率等因素的影响。实验研究结果表明,Bi-Mo/TiO_2对2-甲基吡啶有比较高的...制备了气相催化氧化2-甲基吡啶合成2-吡啶甲醛的双金属Bi-Mo/TiO_2催化剂,采用XRD、H_2-TPR、SEM和XPS对催化剂进行了表征,并考察了催化剂组成、反应温度、原料流率等因素的影响。实验研究结果表明,Bi-Mo/TiO_2对2-甲基吡啶有比较高的催化活性是基于Bi_2Mo_3O_(12)和MoO_3的协同催化作用,Bi2Mo_3O_(12)和MoO_3的较佳摩尔比率为1:1,催化剂的较佳负载量为15%(wt),低反应温度和高原料流率可以提高对2-吡啶甲醛的选择性。较佳反应条件下(反应温度290℃,10%(wt)2-甲基吡啶水溶液的流率为0.5 m L×min-1,氧气的流率为0.1 L×min^(-1),空速12600 h^(-1)),2-甲基吡啶的转化率为70.9%,2-吡啶甲醛的选择性为83.1%。展开更多
AstereodivergentPd/Cucatalyst systemforasymmetric desymmetric alkylation of allylic geminal dicarboxylates has been developed,which was successfully applied to the asymmetric synthesis of β-hydroxycarbonylmotifs bear...AstereodivergentPd/Cucatalyst systemforasymmetric desymmetric alkylation of allylic geminal dicarboxylates has been developed,which was successfully applied to the asymmetric synthesis of β-hydroxycarbonylmotifs bearing a versatile carbon-carbon double bond in an enantio-and diastereodivergent manner.A wide scope of substrates including challenging alkylsubstituted,2-substituted,and3,3′-disubstitutedallylic species are compatible with this catalytic system,delivering the substituted products in high to excellent yieldsandwith excellent diastereo-(upto>20:1 dr)and enantioselectivities(up to>99%ee).Furthermore,the mechanism of this dual Pd/Cu catalytic system including:(1)the desymmetrization process ofgeminal dicarboxylates;(2)the origin of regioselectivity(branched or linear);(3)the enantio-and diastereoselectivity observed by changing the combinations of two chiral metal catalysts,have been carefully investigated by theoretical calculations.展开更多
The construction of distorted or irregular coordination polyhedrons with specific shapes and functionalities is highly challenging.Here,we demonstrate a viable strategy for attaining a severely distorted octahedral co...The construction of distorted or irregular coordination polyhedrons with specific shapes and functionalities is highly challenging.Here,we demonstrate a viable strategy for attaining a severely distorted octahedral coordination container through precise geometrical manipulation of its nanocavity along the C_(3) or C4 axis to turn on its supramolecular catalysis.We constructed a tetragonal-elongated octahedral coordination container utilizing sulfonylcalix[4]arene-capped Co4 units as six vertexes and tetragonalelongated from single-arm lengthened 5-[(4-carboxybenzyl)amino]isophthalate(L)as eight triangular faces.Through the concomitant introduction of C_(3)-symmetry cyclohexane-1,3,5-tricarboxylate as a secondary linker to construct two equilateral triangular base surfaces and L to build six isosceles triangular side planes,trigonal antiprismatic architecture(trigonal-elongated octahedron)was attained.The elongated octahedral containers exhibited distinctly higher binding capacity and stronger binding affinity toward reaction substrates than that of regular octahedral containers;thus,promoting geometry-dependent catalytic reactivity.Our geometrical manipulation strategy provides a viable approach for the convenient design of metal–organic materials with specific functionalities.展开更多
Reductive deoxygenation of ketones using H_(2) is a highly desirable but also challenging transformation in both chemical synthesis,industrial-scale petroleum and biomass feedstock reforming processes.Herein,we report...Reductive deoxygenation of ketones using H_(2) is a highly desirable but also challenging transformation in both chemical synthesis,industrial-scale petroleum and biomass feedstock reforming processes.Herein,we report a cooperative cobalt/Lewis acid (LA)-catalyzed hydrodeoxygenation of ketones using H_(2) as the reductant.In particular,the newly developed pincer cobalt catalyst possesses dual hydrogenation activities for both ketones and alkenes under the same reaction conditions.This reaction features a broad substrate scope,excellent functional-group compatibility,and potential applicability.展开更多
基金the National Natural Science Foundation of China(No.21702189)the Key Scientific and Technological Project of Henan Province(No.202102310004)+1 种基金Science and Technology Research and Development Plan Joint Fund(cultivation of superior disciplines)Project(No.222301420042)Zhengzhou University(No.JC21253007)of China for financial support of this research.
文摘Metal/nucleophilic Lewis base dual catalysis has been recognized as a reliable and promising strategy for finishing ideal organic synthesis over the past decades.The new strategy can usually achieve some chemical reactions that cannot be realized by the traditionally mono-catalytic system,dramatically expanding the synthetic utility of chemical transformations by leveraging additional activation modes.Thus considerable progress has been made in the synthesis of a wide range of heterocyclic and biologically active compounds by using the combination of diversely metal/nucleophilic Lewis base dual catalysts,including metal/phosphine,metal/N-heterocyclic carbene(NHC)and metal/tertiary amine dual catalysis systems.In this review,we describe a comprehensive and updated advance of metal/nucleophilic Lewis base dual catalytic annualtion reactions,meanwhile,the related mechanism and the application of these annulation strategies in natural product total synthesis will be highlighted in detail.
基金supported by the National Natural Science Foundation of China(21971110,21732003)。
文摘Transition metal catalysis is one of the most important tools to construct carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. Visible-light photoredox catalysis has recently drawn considerable attention of the scientific community owing to its unique activation modes and significance for the green synthesis. The merger of photoredox catalysis with transition metal catalysts, termed metallaphotoredox catalysis, has become a popular strategy for expanding the synthetic utility of visiblelight photocatalysis. This strategy has led to the discovery of novel asymmetric transformations, which are unfeasible or not easily accessible by a single catalytic system. This contemporary area of organic chemistry holds promise for the development of economical and environmentally friendly methods for the asymmetric synthesis of chiral compounds. In this review, the advances in the enantioselective metallaphotoredox catalysis(EMPC) are summarized.
基金supported by the National Natural Science Foundation of China(051170001,21772084,22071087)the Fundamental Research Funds for the Central Universities(lzujbky-2017k06)+1 种基金the Open Projects Funds of Shandong Key Laboratory of Carbohydrate Chemistry and Glycobiology,Shandong University(2019CCG05)Xiaolei Wang thanks the Thousand Young Talents Program for financial support。
文摘Herein,we reported the stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis and found a suitable system to resolve many challenges,such as the tolerance towards the density of functional groups,the variability of the anomeric position,the compatibility of appropriate catalyst combinations,the regioselectivity of nucleophiles,and the match/mismatch problems between chiral substrates and chiral ligand-metal complexes.The method enables the efficient preparation of a series of unnatural C-glycosamino acid skeletons bearing two contiguous stereogenic centers in good yields with excellent diastereoselectivity.From this crucial precursor,various C-glycosamino acid derivatives have been achieved diversely.The readily prepared C-glycosamino acid hybrids will meet the growing demands for the development of new molecular entities for discovering new drugs and materials.This stereodivergent synthesis of C-glycosamino acids will further accelerate the study of their structural features,mode of action,and potential biological applications in the near future.
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21871112 and 21971090).
文摘A new dual plldium/scandium catalysis starting fromβ-alkynyl ketones and o alkynyl anilines is reported for the first time,leading to the atom-economic synthesis of rotationally hindered C3-naphthylated indoles in moderate to good yields and high regioselectivi-ty.This method can tolerate normal air conditions,and features the use of palladium/scandium cooperative catalysts without any ligand,facile double annulation involving various internal alkynes,and good functional group tolerance.
文摘A new process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high catalytic promoting effect on the synthesis of methanol from CO hydrogenation. At 443 K and 5 MPa, the synthesis of methanol could process high effectively, resulting from the synergic catalysis of Cu/ZnO solid catalyst and 2-alcohol solvent catalyst. The primary results showed that when 2-butanol was used as reaction solvent, the one-pass average yield and the selectivity of methanol, in 40 h continuous reaction at temperature as low as 443 K and 5 MPa, were high up to 46.51% and 98.94% respectively. The catalytic activity was stable and the reaction temperature was 80 K or so lower than that in current industry synthesis process. This new process hopefully will become a practical method for methanol synthesis at low temperature.
基金supported by the National Basic Research Program of China (973 Program 2011CBA00501)+2 种基金Shanghai Municipal Science and Technology Commission China (11DZ1200300)the Foundation of State Key Laboratory of Coal Conversion (11‐12‐610)~~
文摘制备了气相催化氧化2-甲基吡啶合成2-吡啶甲醛的双金属Bi-Mo/TiO_2催化剂,采用XRD、H_2-TPR、SEM和XPS对催化剂进行了表征,并考察了催化剂组成、反应温度、原料流率等因素的影响。实验研究结果表明,Bi-Mo/TiO_2对2-甲基吡啶有比较高的催化活性是基于Bi_2Mo_3O_(12)和MoO_3的协同催化作用,Bi2Mo_3O_(12)和MoO_3的较佳摩尔比率为1:1,催化剂的较佳负载量为15%(wt),低反应温度和高原料流率可以提高对2-吡啶甲醛的选择性。较佳反应条件下(反应温度290℃,10%(wt)2-甲基吡啶水溶液的流率为0.5 m L×min-1,氧气的流率为0.1 L×min^(-1),空速12600 h^(-1)),2-甲基吡啶的转化率为70.9%,2-吡啶甲醛的选择性为83.1%。
基金supported by the National Natural Science Foundation of China(nos.21620102003,21831005,21901158,and 21991112)the Shanghai Sailing Program(no.19YF1421900)+3 种基金Shanghai Municipal Education Commission(no.201701070002E00030)National Key R&D Program of China(no.2018YFE0126800)the Science and Technology Commission of Shanghai Municipality(no.19JC1430100)Zhiyuan Scholar Program(no.ZIRC2020-04).
文摘AstereodivergentPd/Cucatalyst systemforasymmetric desymmetric alkylation of allylic geminal dicarboxylates has been developed,which was successfully applied to the asymmetric synthesis of β-hydroxycarbonylmotifs bearing a versatile carbon-carbon double bond in an enantio-and diastereodivergent manner.A wide scope of substrates including challenging alkylsubstituted,2-substituted,and3,3′-disubstitutedallylic species are compatible with this catalytic system,delivering the substituted products in high to excellent yieldsandwith excellent diastereo-(upto>20:1 dr)and enantioselectivities(up to>99%ee).Furthermore,the mechanism of this dual Pd/Cu catalytic system including:(1)the desymmetrization process ofgeminal dicarboxylates;(2)the origin of regioselectivity(branched or linear);(3)the enantio-and diastereoselectivity observed by changing the combinations of two chiral metal catalysts,have been carefully investigated by theoretical calculations.
基金supported by the National Natural Science Foundation of China(grant nos.21673239,21501179,and 21531008)Natural Science Foundation of Fujian Province(grant no.2017J06008)+1 种基金the CAS/SAFEA International Partnership Program for Creative Research Teams,and the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB20000000)Z.W.acknowledges a National Science Foundation CAREER award(grant no.CHE-1352279)for supporting work related to the design and synthesis of container molecules,a second NSF grant(grant no.CHE-1800354)for supporting work pertaining to supramolecular catalysis,and the South Dakota Governor’s Office of Economic Development through the Center for Fluorinated Functional Materials for additional financial support.
文摘The construction of distorted or irregular coordination polyhedrons with specific shapes and functionalities is highly challenging.Here,we demonstrate a viable strategy for attaining a severely distorted octahedral coordination container through precise geometrical manipulation of its nanocavity along the C_(3) or C4 axis to turn on its supramolecular catalysis.We constructed a tetragonal-elongated octahedral coordination container utilizing sulfonylcalix[4]arene-capped Co4 units as six vertexes and tetragonalelongated from single-arm lengthened 5-[(4-carboxybenzyl)amino]isophthalate(L)as eight triangular faces.Through the concomitant introduction of C_(3)-symmetry cyclohexane-1,3,5-tricarboxylate as a secondary linker to construct two equilateral triangular base surfaces and L to build six isosceles triangular side planes,trigonal antiprismatic architecture(trigonal-elongated octahedron)was attained.The elongated octahedral containers exhibited distinctly higher binding capacity and stronger binding affinity toward reaction substrates than that of regular octahedral containers;thus,promoting geometry-dependent catalytic reactivity.Our geometrical manipulation strategy provides a viable approach for the convenient design of metal–organic materials with specific functionalities.
基金Financial support from the National Key R&D Program of China(2021YFF0701600)the National Natural Science Foundation of China(22225103)Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs,Shanghai Jiao Tong University is greatlyappreciated.
文摘Reductive deoxygenation of ketones using H_(2) is a highly desirable but also challenging transformation in both chemical synthesis,industrial-scale petroleum and biomass feedstock reforming processes.Herein,we report a cooperative cobalt/Lewis acid (LA)-catalyzed hydrodeoxygenation of ketones using H_(2) as the reductant.In particular,the newly developed pincer cobalt catalyst possesses dual hydrogenation activities for both ketones and alkenes under the same reaction conditions.This reaction features a broad substrate scope,excellent functional-group compatibility,and potential applicability.
