Article
Chemistry, Organic
Timothy P. Aldhous, Raymond W. M. Chung, Andrew G. Dalling, John F. Bower
Summary: This review presents recent intermolecular enantioselective Murai-type alkene hydroarylation methodologies and the mechanisms by which they proceed, providing an efficient way to achieve enantioselective hydroarylations of alkenes with benzylic stereocenters.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Jiang-Fei Li, Yu-Xin Luan, Mengchun Ye
Summary: Anchoring catalysis involves a reversible interaction between substrates and catalysts to activate inert chemical bonds without the need for preinstalled directing groups. Coordinative bimetallic anchoring catalysis, in particular, displays superior reactivity due to strong interaction and good compatibility with substrates and reaction conditions. Major progress has been made in recent years in the development of coordinative bimetallic anchoring catalysis.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Physical
Xiaoliang Zou, Yinwu Li, Zhuofeng Ke, Senmiao Xu
Summary: Ferrocenes with planar chirality are important for various chiral ligands and organocatalysts. This study reports an iridium-catalyzed enantioselective dual C-H borylation of ferrocenes using an amide directing group. The reaction showed high enantioselectivity and tolerance towards different functional groups.
Article
Chemistry, Physical
Jinlei Wang, Haohua Chen, Lingheng Kong, Fen Wang, Yu Lan, Xingwei Li
Summary: This report describes a method for introducing distally disposed axial and central chirality via rhodium-catalyzed C-H alkylation of benzamides using N-arylmaleimide as the alkylating reagent. The process features excellent enantio- and diastereoselectivity, broad substrate scope, and mild reaction conditions. Chiral induction is achieved through the judicious choice of a chiral rhodium cyclopentadienyl catalyst.
Article
Chemistry, Multidisciplinary
Yanjun Li, Yan-Cheng Liou, Joao C. A. Oliveira, Lutz Ackermann
Summary: The successful ruthenium(II)-catalyzed highly regio-, diastereo- and enantioselective C-H alkylation by using novel C2-symmetric chiral ligands demonstrated high efficiency and excellent chiral molecule construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Tatsuhiro Uchikura, Sotaro Kato, Yudai Makino, Megumi J. J. Fujikawa, Masahiro Yamanaka, Takahiko Akiyama
Summary: Desymmetrization is a crucial technique for synthesizing chiral compounds, especially chiral biaryls. This study presents an enantioselective synthesis of axially chiral biaryls through desymmetrization using chiral palladium phosphate as the catalyst for C(sp(3))-H activation. Mechanistic investigations reveal that C-H activation plays a crucial role in determining the rate and enantiomeric selectivity. To the best of our knowledge, this is the first report on the asymmetric desymmetrization of axially chiral compounds via C(sp(3))-H activation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Physical
Prabhat Kumar Baroliya, Jaishri Chopra, Tanay Pal, Siddhartha Maiti, Shaeel Ahmed Al-Thabaiti, Mohamed Mokhtar, Debabrata Maiti
Summary: Supported metal nanoparticles have become an essential research area in catalysed chemical transformations, providing sustainable processes and efficient tuning of reactivity and recyclability. Various support materials have been investigated for their benefits in C-H functionalization, aiming to design efficient catalytic systems for future research.
Review
Chemistry, Multidisciplinary
Karunanidhi Murali, Luana A. Machado, Renato L. Carvalho, Leandro F. Pedrosa, Rishav Mukherjee, Eufranio N. Da Silva Junior, Debabrata Maiti
Summary: C-H functionalization has made significant advancements in synthetic organic chemistry, offering promising prospects in drug development and molecular architecture. The employment of novel metal catalysts and metal-free organic ligands has enabled selective activation of C-H bonds, overcoming previous challenges faced by chemists.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Ye Lin, Tristan von Muenchow, Lutz Ackermann
Summary: 3D metallaelectro-catalyzed C-H activation is a promising strategy to obtain valuable organic molecules in an economically and environmentally friendly manner. However, achieving enantioselective C-H activation using 3D metals is challenging and has limited progress. In this study, we combined cobaltaelectro-catalyzed C-H activation with asymmetric catalysis to achieve highly enantioselective annulation of allenes, resulting in a wide range of chiral compounds with good yields and high enantioselectivities. This approach demonstrated practicality by diversifying complex bioactive compounds and drug molecules, as well as conducting large-scale enantioselective electrocatalysis in continuous flow.
Review
Chemistry, Organic
Alessia Mori, Sebastien Curpanen, Cristofer Pezzetta, Alejandro Perez-Luna, Giovanni Poli, Julie Oble
Summary: Furfural and related compounds, as building blocks of industrial interest, have gained attention as green alternatives to petroleum-derived compounds. This minireview summarizes the methods of direct C-H functionalization of furfurals without modifying the redox state of the aldehyde function, focusing on transition metal catalyzed functionalization of the heteroaromatic nucleus and C-H transformations of the aldehyde function.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Princi Gupta, Suchithra Madhavan, Manmohan Kapur
Summary: In this study, a method for distal C-H functionalization of monosubstituted ferrocenes using an easily removable directing group under a Pd-II/ mono-N-protected amino-acid ligand catalytic system is reported. The synthetic protocol allows for the synthesis of ferrocene 1,3-derivatives with broad scope in olefins, by functionalizing ferrocenyl methylamine in moderate to good yields through a highly strained ferrocene appended 12-membered palladacycle intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Applied
Xiaofan Cui, Remi Chauvin, Chao Pi, Yangjie Wu, Xiuling Cui
Summary: This review presents recent progress in the use of vinylene carbonate as a reactant in transition metal-catalyzed C-H bond activation/cyclization reactions. By analyzing and comparing different reaction models, it highlights the advantages of using vinylene carbonate as a surrogate for ethynol and other reactants, and discusses related mechanisms and synthetic applications.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Marc Font, Moises Gulias, Jose Luis Mascarenas
Summary: The selective functionalization of C(sp(3))-H bonds using transition-metal catalysis is an important transformation in modern synthetic chemistry, although it poses significant challenges. There has been notable progress in recent years, particularly in the development of new intermolecular reactions. Conversely, the research on assembling cyclic products from simple acyclic precursors using metal-catalyzed C(sp(3))-H bond activations has been relatively limited.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Nelson Y. S. Lam, Kevin Wu, Jin-Quan Yu
Summary: The design of synthetic routes by retrosynthetic logic is influenced by available transformations. Transition-metal-catalyzed C-H activation is a powerful strategy for C-C bond formation, but its uptake in total synthesis has been tepid due to synthetic intractability and a lack of comprehensive guidelines. This Review addresses these issues and offers a guide to identify retrosynthetic opportunities to generate C-C bonds by C-H activation processes. Comparing traditional approaches and recent C-H activation methods, this Review demonstrates more efficient retrosynthetic strategies enabled by C-H activation for C-C bond construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Pablo Vazquez-Dominguez, Antonio Romero-Arenas, Rosario Fernandez, Jose Maria Lassaletta, Abel Ros
Summary: The catalytic hydroarylation of alkynes is a useful method for synthesizing functionalized alkenes with excellent control of regio- and stereochemistry. However, there is a scarcity of asymmetric methodologies in this field. In this study, an atroposelective Ir-catalyzed C-H hydroarylation of alkynes was developed, enabling the asymmetric synthesis of axially chiral heterobiaryl trisubstituted olefins with high yields and enantioselectivities up to 98% ee.
Article
Chemistry, Physical
Zheng-Bing Zhang, Yusheng Yang, Zhi-Xiang Yu, Ji-Bao Xia
Article
Chemistry, Multidisciplinary
Wen-Duo Li, Jie Chen, Dao-Yong Zhu, Ji-Bao Xia
Summary: This study introduces a novel cyclization reaction using CO2 as a sustainable C1 feedstock and iron as catalyst, achieving selective reduction into methylene intermediate under carefully tuned reaction parameters. Various nitrogen-containing heterocycles can be easily obtained under mild conditions, possibly via spiroindolenine intermediates.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Yan-Lin Li, Zheng-Yang Gu, Ji-Bao Xia
Summary: The amide linkage is a crucial structural moiety in chemistry and biology. Recent advances in catalytic intermolecular C-H carbonylation reactions, particularly the intermolecular C-H amidation of arenes with carbon monoxide and organic azides for amide synthesis, are discussed.
Article
Chemistry, Physical
Xiao Guo, Yang Wu, Gongqiang Li, Ji-Bao Xia
Article
Chemistry, Organic
Zheng-Yang Gu, Yang Wu, Feng Jin, Xiaoguang Bao, Ji-Bao Xia
Summary: The atom- and step-economic intermolecular multi-component palladium-catalyzed C-H amidation of alkenes with carbon monoxide and organic azides has been successfully developed for the synthesis of alkenyl amides without an ortho-directing group on the alkene substrates. The reaction generates nontoxic dinitrogen as the sole by-product, and computational studies and control experiments have revealed an unexpected mechanism by tandem palladium catalysis.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Yan-Lin Li, Shi-Qi Zhang, Jie Chen, Ji-Bao Xia
Summary: A highly regio- and enantioselective reductive coupling of alkynes and aldehydes has been developed under visible light photoredox dual catalysis, providing enantioenriched allylic alcohols with excellent selectivity control and broad substrate scope. This approach shows considerable advantages, making significant improvements to enantioselective alkyne-aldehyde reductive coupling reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yi-Qian Jiang, Zheng-Yang Gu, Ye Chen, Ji-Bao Xia
Summary: This method efficiently converts silyl enol ethers to beta-ketoamides using Pd catalyst, carbon monoxide, and sulfonyl azides, providing a simple and direct approach for synthesis under mild conditions. Mechanistic studies suggest that the reaction proceeds through an in situ generated isocyanate intermediate.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Wen-Duo Li, Yi-Qian Jiang, Yan-Lin Li, Ji-Bao Xia
Summary: A new approach for the radical cross coupling of organic halides and oxalates toward esters has been developed using photoredox nickel dual catalysis. This method allows for the transformation of a wide range of bromides to esters under mild conditions, including aryl, heteroaryl, alkenyl, and alkyl bromides. The selective coupling of alkoxycarbonyl radicals over decarboxylative alkyl radicals has been achieved, making it a convenient method for the synthesis of drug molecules from simple aryl dihalides.
Article
Chemistry, Multidisciplinary
Wen-Duo Li, Yang Wu, Shi-Jun Li, Yi-Qian Jiang, Yan-Lin Li, Yu Lan, Ji-Bao Xia
Summary: A new strategy for direct cleavage of the C(sp3)-OH bond has been developed using neutral diphenyl boryl radical to activate free alcohols. Under mild visible light photoredox conditions, this strategy has been verified by cross-electrophile coupling of free alcohols and carbon dioxide to synthesize carboxylic acids. Control experiments and computational studies have shown that the activation of alcohols with neutral boryl radical leads to homolysis of the C(sp3)-OH bond, generating alkyl radicals, which can be further transformed into carbon anions for carboxylation with CO2 to form the coupling product.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zheng-Yang Gu, Wen-Duo Li, Yan-Lin Li, Kun Cui, Ji-Bao Xia
Summary: A visible light-induced Co-catalyzed reductive coupling reaction has been developed for the highly selective synthesis of multiple substituted alkenes with an azaarene motif. This approach, utilizing Hunig's base and ethanol as hydrogen sources, offers excellent regio- and stereoselectivity, broad substrate scope, and good functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kun Cui, Yan-Lin Li, Gongqiang Li, Ji-Bao Xia
Summary: A new regio- and stereoselective reductive coupling of alkynes and crotononitrile has been developed using visible light organophotoredox cobalt dual catalysis, resulting in the synthesis of enantioenriched homoallylic nitriles with stereodefined trisubstituted alkene.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Chao Yang, Lijun Shi, Fang Wang, Yijin Su, Ji-Bao Xia, Fuwei Li
Summary: In this study, we report a method of synthesizing chiral compounds with stereogenic bridgehead quaternary stereocenters through asymmetric catalysis of alkenylamides and alkynes. The reaction achieved high stereoselectivity and moderate-to-good yields.
Article
Chemistry, Organic
Chao Yang, Lijun Shi, Wenlong Wang, Ji-Bao Xia, Fuwei Li
Summary: The well-developed carbonylative synthesis of varied and useful complex molecules with CO is achieved through the rhodium-catalyzed modular carbonylative aminobenzoylation of alkenes with acylaniline under ambient pressure of CO/O-2. The reaction involves the dual cleavage of N-H and C-H bonds and provides moderate-to-high yields of various poly(hetero)cyclic alkylarylketones. The synthetic transformations of the products were also investigated.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Zheng-Yang Gu, Ji-Bao Xia
Summary: A efficient [3 + 1 + 1] cyclization of vinyl oxiranes has been developed for the synthesis of oxazolidinones via tandem palladium catalysis. This reaction provides an atom- and step-efficient strategy to produce oxazolidinones from readily available azides and carbon monoxide under mild additive- and base-free conditions. Mechanistic studies demonstrated that the reaction occurred through an in situ generated isocyanate intermediate.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Zheng-Yang Gu, Hui Han, Zi-Yin Li, Shun-Jun Ji, Ji-Bao Xia
Summary: This method utilizes amines, isocyanides, and diazo compounds as carbene sources to provide a synthetic simple and highly efficient strategy for the straightforward synthesis of functionalized amidines with a range of substrates.
ORGANIC CHEMISTRY FRONTIERS
(2021)
