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, Applied
Pidiyara Karishma, Alisha Gogia, Sanjay K. Mandal, Rajeev Sakhuja
Summary: This study successfully achieved a direct carbocyclization of 2-aryl-2,3-dihydrophthalazine-1,4-diones using isocyanates as the carbonyl source via Ru(II)-catalyzed sequential ortho-amidation followed by intramolecular nucleophilic substitution, delivering substituted indazolo[1,2-b]phthalazine-triones in good-to-excellent yields. Additionally, excellent yields of the corresponding amidated products were obtained for ortho-substituted 2-aryl-2,3-dihydrophthalazine-1,4-diones by modifying the reaction parameters. The use of isocyanates as the carbonyl source, high functional group tolerance on the two coupling partners, and diverse chemical transformation of the synthesized fused and functionalized phthalazinones are the key highlights of this work.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
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)
Review
Chemistry, Organic
Qijing Zhang, Chengming Wang
Summary: Metal/metal dual catalysis offers new perspectives and opportunities in C-H functionalization, particularly in terms of reactivity and selectivity control.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Mengwei Li, Junjun Shan, Georgios Giannakakis, Mengyao Ouyang, Sufeng Cao, Sungsik Lee, Lawrence F. Allard, Maria Flytzani-Stephanopoulos
Summary: In this work, a one-step conversion of methane to methanol using molecular oxygen as the oxidant in aqueous solutions with the presence of CO on copper or palladium-promoted Ir-ZSM-5 catalyst is reported. The addition of a second metal to Ir-ZSM-5 enhances catalyst activity and tunes product selectivity. The trimetallic system IrCuPd shows the best performance for methanol formation with good stability in cyclic operation.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Review
Chemistry, Applied
Priyanka Chaudhary, Jeyakumar Kandasamy, Allan Patrick G. Macabeo, Ramuel John Inductivo Tamargo, Yong Rok Lee
Summary: This review explores the recent advancements in the C-H functionalization of N-nitrosoanilines, highlighting the versatility of nitroso group as a directing group for ortho C-H activation and introducing various functional groups to generate aromatic derivatives with diverse properties. The reaction mechanisms for different transition metal-catalyzed functionalizations are discussed in detail, showcasing their potential for synthesizing valuable intermediates and unique heterocyclic compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Lu-Lu Han, Yu-Ming Cui, Qin Yang, Li-Lei Fang, Li-Wen Xu
Summary: Palladium-catalyzed asymmetric C-H functionalization and Heck reactions are important strategies for synthesizing quaternary stereocenters. However, developing enantioselective Pd-II-catalyzed cascade reactions remains challenging. In this study, an unprecedented [3+2] annulation of oxime ethers and alkynes was developed, providing spiro and nonspiro indenes with all-carbon quaternary stereocenters in high yields and excellent enantioselectivities. This annulation was achieved by combining atroposelective C-H activation/double carbopalladation and transient axial-to-central chirality transfer, representing a successful catalytic chirality transfer strategy involving axially chiral styrene intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Prabhat Kumar Baroliya, Mukesh Dhaker, Subir Panja, Shaeel Ahmed Al-Thabaiti, Soha M. Albukhari, Qana A. Alsulami, Arnab Dutta, Debabrata Maiti
Summary: Electrochemically promoted transition metal-catalyzed C-H functionalization is a promising area of research, but it is still at an early stage compared to traditional chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically promoted metal-catalyzed C-H functionalization. From the perspective of sustainability and cost effectiveness, electrochemically promoted oxidation of a metal catalyst offers a mild, efficient, and atom-economical alternative to traditional chemical oxidants. This Review discusses advances in the field of transition metal-electrocatalyzed C-H functionalization and how electricity enables metal-catalyzed C-H functionalization in an economic and sustainable way.
Article
Chemistry, Organic
Zhangqiang Yan, Zhen Zhang, Tao Wen, Lihua Ye, Bo Jin, Chihong Zhang, Wenkun Wang, Zhong-Ning Chen, Hu Cai
Summary: Direct alpha-C(sp(3))-H alkylation of hydroaminoalkylation (HAA) catalyzed by (BuOK)-Bu-t/DMSO/O-2 from alpha-aryl benzylamines with styrenes was reported. The reaction provided selectively substituted amines and N-heterocycles under mild conditions. Mechanism studies revealed that alpha-aminoalkyl radicals acted as intermediates and hydrogen atom transfer (HAT) played a crucial role in the (BuOK)-Bu-t/DMSO/O-2 system.
ORGANIC CHEMISTRY FRONTIERS
(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
Sumon Basak, Subhabrata Dutta, Debabrata Maiti
Summary: The skeletal presence of 1,3-azoles in various bioactive compounds necessitates regioselective derivatization, with transition metal-catalyzed C-H functionalization emerging as a superior alternative to traditional methods. Recent research on C-2 functionalization of 1,3-azoles has shown significant progress in achieving high regioselectivity and introducing synthetically manipulative functionalities.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Juba Ghouilem, Morgane de Robichon, Franck Le Bideau, Angelique Ferry, Samir Messaoudi
Summary: Transition-metal-catalyzed C-H functionalization and photoredox nickel dual catalysis are innovative approaches for the synthesis of C-branched glycosides, providing efficient and mild methods for accessing a variety of complex C-branched glycosides of great interest.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Ke-Xin Wu, Yi-Ze Xu, Liang Cheng, Run-Shi Wu, Peng-Ze Liu, Da-Zhen Xu
Summary: This paper describes a method for directly constructing all-carbon quaternary centers from secondary C(sp(3))-H substrates through a dehydrogenative cross-coupling reaction, using FeCl2 center dot 4H(2)O as the catalyst and air as the terminal oxidant. This method provides 3,3-disubstituted oxindoles bearing all-carbon quaternary centers with excellent chemoselectivities under mild, ligand-free and base-free conditions.
Review
Chemistry, Multidisciplinary
Sandeep Kumar, Akshay Kumar, Dharminder Sharma, Pralay Das
Summary: Directing groups are widely used for transition metal-catalyzed direct C-H bond functionalization, with recent advancements in utilizing free amine, hydroxyl and sulfhydryl as directing groups for the synthesis of heterocycles.
Article
Chemistry, Physical
Gaurav Kumar, Soumya Ranjan Dash, Subhadip Neogi
Summary: By combining photoredox and organo-catalysis methods, a new approach for constructing carbon-carbon bonds on a two-dimensional porous organic framework has been developed. The catalyst, using oxygen as the oxidant and visible light as the trigger, can successfully synthesize biorelevant products at room temperature, showing excellent reusability and economic viability.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Organic
Qin Wang, Yan Shi, Xiaoli Huang, Yongzhuang Wang, Jiao Jiao, Yuhai Tang, Jing Li, Silong Xu, Yang Li
Summary: A highly efficient Ru(II)-catalyzed regio- and stereospecific hydro-oxycarbonylation reaction has been developed for unsymmetrical internal alkynes bearing a difunctional 2-pyridyloxy directing group with carboxylic acids. This reaction provides allylic (Z)-enol esters in good to excellent yields with a broad substrate scope under mild conditions. The difunctional directing group can be diversely derivatized, particularly allowing for allylic substitution with various nucleophiles to afford beta-functionalized (Z)-enol esters without directing groups.
Article
Chemistry, Organic
Yang Li, Yongzhuang Wang, Xiaoli Huang, Yan Shi, Yuhai Tang, Jiao Jiao, Jing Li, Silong Xu
Summary: This highly efficient cascade cyclization reaction features a Ru(II)-catalyzed C-H activation initiated indole formation/Diels-Alder reaction/iminium ion cyclization sequence, providing hexacyclic indolines as single diastereomer in good to excellent yields with a broad substrate scope under mild conditions. The reaction allows for the simultaneous generation of five new chemical bonds and four new rings in one pot, offering a rapid and concise approach toward synthesizing polycyclic indoline alkaloids and their analogues.
Article
Chemistry, Organic
Lijuan Qiao, Xin He, Lulu Yang, Kaki Raveendra Babu, Yong Wu, Yuhai Tang, Silong Xu
Summary: This study describes a DMAP-catalyzed [3+3] annulation reaction that synthesizes 2-pyrones through the reaction of cyclopropenones with alpha-bromoketones. The method is simple, convenient, and offers high yields with a wide scope of applicability. The reaction benefits from transition metal-free conditions, readily available starting materials, and excellent regioselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Dongqiu Li, Fang Cheng, Yuhai Tang, Jing Li, Yang Li, Jiao Jiao, Silong Xu
Summary: In this study, we describe a DABCO-catalyzed [4 + 2] annulation reaction between 5-methylenehex-2-ynedioates and electron-deficient olefins, which leads to the formation of functionalized cyclohexadienes in good yields under mild reaction conditions. The incorporation of the beta- and epsilon-carbons of the substrates for C-C bond formation represents a novel reactivity different from previous reports. It is believed that the annulation proceeds through a domino cyclization initiated by a cross Rauhut-Currier reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ansar Abbas, Chen Zhang, Sameer Hussain, Yang Li, Ruixia Gao, Jing Li, Xueyi Liu, Minghui Zhang, Silong Xu
Summary: Controlling the stability of oil-in-water emulsions is a key focus for scientists studying colloidal systems. Carbon dots have gained significant interest as smart materials due to their exceptional physicochemical properties and versatile applications. This study presents advanced and switchable O/W emulsions stabilized by the combined effect of the cationic surfactant CTAB and similarly charged CDs. The formulated emulsion shows universal stabilizing effects for a range of oil phases and can be switched between stable and unstable modes by adding anionic surfactant SDBS, with potential applications in water purification, pharmaceuticals, protein recognition, and catalysis.
Article
Chemistry, Physical
Ni Xiong, Yang Li, Rong Zeng
Summary: We have developed a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. By merging iron-catalyzed decarboxylation with copper catalysis, this system allows efficient conversion of a wide range of aliphatic carboxylic acids for various reactions. The strategy has applications in compound library synthesis and the discovery of pharmaceutical agents.
Article
Chemistry, Organic
LuLu Yang, Xin He, Jiao Jiao, Yuhai Tang, Jing Li, Yang Li, Ruixia Gao, Yong Wu, Silong Xu
Summary: This study investigates a phosphine-catalyzed ring-opening addition reaction of cyclopropenones with various nucleophiles, generating potentially useful alpha,beta-unsaturated carbonyl derivatives with high yields (up to 99%), high regioselectivity, and exclusive E-selectivity. The reaction demonstrates high efficiency under very mild conditions, utilizing only 1 mol % PPh3 catalyst at room temperature. The method is also applicable for the synthesis of deuterated alkenes using deuterated nucleophiles (NuD). Experimental and DFT calculations indicate that an alpha-ketenyl phosphorus ylide serves as a key intermediate in the catalytic cycle, selectively capturing nucleophiles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yan Shi, Cui Yi, Xiaoli Huang, Yuhai Tang, Jiao Jiao, Yang Li
Summary: A highly efficient cross-dehydrogenative aromatization of cyclohexenones with amines has been developed using iodine anion as the catalyst under metal-free conditions. This reaction provides aromatic amines in good to excellent yields with a broad substrate scope. It also offers a new method for constructing C(sp(2))-N bonds and a strategy for in situ dehalogenation to generate oxidants or electrophiles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fang Cheng, Dongqiu Li, Jing Li, Yuhai Tang, Yong Wu, Silong Xu
Summary: In this study, a phosphorus-containing species was used as a radical precursor to catalytically synthesize phosphinic amides without generating phosphorus waste. The proposed mechanism involves the formation of a R2N-O-PR2 species, followed by homolysis of N-O bonds and subsequent radical recombination.
Article
Chemistry, Organic
Dongqiu Li, Xiaoqian Zhang, Wendan Han, Jiao Jiao, Yuhai Tang, Silong Xu
Summary: This study presents a Lewis base-catalyzed annulation reaction using hepta-2,3,5-trienedioates as substrates. Mild conditions allow for the construction of exocyclic olefinic cyclopentenes through a [3+2] annulation with electron-deficient alkenes, obtaining good yields and moderate E:Z ratios. This reaction involves a tandem [3+2] cyclization and double bond migration, with the ε-ester playing a crucial role in both processes. Additionally, it demonstrates a substrate-controlled divergent reactivity compared to a previous report.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ni Xiong, Yang Li, Rong Zeng
Summary: We present a dual catalytic strategy for the functionalization of aliphatic carboxylic acids using photoinduced iron/copper catalysts. The photoinduced ligand-to-iron charge transfer process generates an unstabilized alkyl radical, which is then utilized by the copper catalyst for coupling reactions to form C-N or C-C bonds. This system enables efficient conversion of a wide range of aliphatic carboxylic acids and has potential applications in drug discovery.
Article
Chemistry, Multidisciplinary
Xin He, Pengchen Ma, Yuhai Tang, Jing Li, Shenyu Shen, Martin J. Lear, K. N. Houk, Silong Xu
Summary: We report a phosphine-catalyzed (3 + 2) annulation of cyclopropenones with various electrophilic pi systems, yielding products including butenolides, butyrolactams, maleimides, and iminomaleimides in high yields with a wide range of substrates. An alpha-ketenyl phosphorous ylide is identified as the key intermediate, which undergoes preferential catalytic cyclization with aldehydes. This phosphine-catalyzed activation of cyclopropenones provides a versatile C-3 synthon for formal cycloadditon reactions.
Article
Chemistry, Multidisciplinary
Huijia Song, Feng Wang, Yayun Zhao, Ruixia Gao, Yulian He, Qing Yan, Xiaoyi Chen, Lisa D. Pfefferle, Silong Xu, Ying Sheng
Summary: This article proposes a method for simultaneous detection of dual biomarkers based on anti-interference magnetic molecularly imprinted polymers, which has been successfully applied in the detection of Parkinson's disease bio-indicators DOPAC and DA in human urine. The method exhibits good anti-interference, high accuracy, and fast batch detection.
