Article
Chemistry, Physical
Rahul K. Shukla, Atul K. Chaturvedi, Chandra M. R. Volla
Summary: A Pd(II)-catalyzed directed, regio-controlled hydroheteroarylation of unactivated alkenes has been developed for the construction of gamma-heteroaryl-substituted carbonyl compounds. The methodology is operationally simple and compatible with a variety of nucleophiles to deliver structurally divergent heterocyclic skeletons. This approach also demonstrated synthetic utility in gram-scale synthesis, directing group removal, and late-stage modification of drugs and natural products.
Article
Chemistry, Multidisciplinary
Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu
Summary: A novel method for constructing amide bonds through anti-Markovnikov hydroaminocarbonylation of unactivated alkenes has been developed. Copper catalysis, hydroxylamine electrophile reagents, and poly(methylhydrosiloxane) (PMHS) were used under mild conditions. The reaction showed a high degree of tolerance towards various functional groups and efficiently converted unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu
Summary: This paper reports a general method for the anti-Markovnikov hydroaminocarbonylation of unactivated alkenes under mild conditions, using copper catalysis in combination with hydroxylamine electrophile reagents and poly(methylhydrosiloxane) (PMHS) as a cheap and environmentally friendly hydride source. The reaction tolerates a variety of functional groups and efficiently converts unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity (and high enantioselectivities/diastereoselectivities). Additionally, with minimal modification of the reaction conditions, alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation to alkyl amides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jingqiang Han, Huimin Yu, Weiwei Zi
Summary: This study reported a regioselective hydroarylation reaction of unactivated alkenes with aryl boronic acids directed by carboxylic acid. The reaction was achieved by using a homogeneous manganese catalyst MnBr(CO)(5) in the presence of KOH and H2O in the m-xylene reaction medium. Both internal and terminal alkenes showed good reactivity in this transformation, and a variety of functional groups were tolerated.
Article
Chemistry, Organic
Young Ho Kim, Dong Bin Kim, Su San Jang, So Won Youn
Summary: A Pd-catalyzed intramolecular allylic C-H amination method has been developed, allowing for the synthesis of diverse 1,3-X,N-heterocycles through selective allylic C-H cleavage and pi-allylpalladium formation. The use of substrates containing a labile allylic moiety and new catalytic systems overcomes significant challenges for achieving highly chemo- and regioselective allylic C-H amination.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Jinwei Sun, Yongze Zhou, Rui Gu, Xin Li, Ao Liu, Xuan Zhang
Summary: Here, the authors report a nickel-catalyzed method for the silylative alkylation of activated olefins using chlorosilanes and alkyl bromides. This approach enables the efficient synthesis of alkylsilanes with diverse structures and demonstrates good functional group tolerance. The method can also be applied for the functionalization of bioactive molecules.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Km Ishu, Dharmendra Kumar, Naveen Kumar Maurya, Suman Yadav, Dhananjay Chaudhary, Malleswara Rao Kuram
Summary: A palladium-catalyzed domino Heck/intermolecular direct hetero arylation sequence of unactivated alkenes was developed in this study, providing bisheterocycles bearing all-carbon quaternary centers with 1,2,3-triazole moiety in yields of 25-90%. The protocol was also successfully extended to 1,3,4-oxadiazoles, and the installed triazole was further utilized for late-stage functionalizations, with mechanistic studies pointing towards the involvement of C-H activation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Physical
Lang Cheng, Qi Tang, Ya-Mei Dai, Bi-Qin Wang, Ping Hu, Peng Cao, Feijie Song
Summary: The Rh-catalyzed intramolecular hydroarylation of olefin-tethered benzocyclobutenols via C-C bond activation has been achieved, providing an alternative approach to 3,3-disubstituted 2,3-dihydrobenzofurans bearing a 4-beta-keto moiety. The methodology features 100% atom economy and pH-and redox-neutral conditions, and is applicable to the late-stage functionalization of complex molecules. The asymmetric variant has also been achieved with excellent enantioselectivities.
Article
Chemistry, Multidisciplinary
Lanlan Zhang, Chun Luo, Haoran Shi, Lin Zhu, Yuan-Qing Xu, Zhong-Yan Cao, Chao Wang
Summary: A practical method for regioselective hydroarylation of unactivated gamma- or delta-vinyl alkylamines has been reported, allowing for the facile preparation of highly value-added epsilon- or zeta-aryl alkylamines. The protocol employs nickel catalysis, exhibits high functional group tolerance, and can be utilized for modifying bio-related molecules.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Balaji D. Barve, Yao-Haur Kuo, Wen-Tai Li
Summary: The use of bulky ligands can enhance the reductive elimination pathway and inhibit beta-hydride elimination, leading to the selective formation of difunctionalized alkene products.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Chuanqi Hou, Pinhong Chen, Guosheng Liu
Summary: This study reports a palladium-catalyzed Markovnikov hydroalkynylation reaction for the synthesis of branched alkynyl compounds. The reaction shows excellent functional group tolerance, high reaction yields, and good regioselectivity. Moreover, asymmetric hydroalkynylation has been achieved by introducing a chiral ligand.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Rahul K. Shukla, Atul K. Chaturvedi, Subir Pal, Chandra M. R. Volla
Summary: In this study, a Pd(II)-catalyzed regioselective hydrocarbofunctionalization of unactivated alkenes was demonstrated. The regioselectivity of the reaction was controlled by using a bidentate auxiliary and specific alkynes, leading to the formation of 1,6-dicarbonyl compounds through a cascade sequence.
Article
Chemistry, Multidisciplinary
Dong-Tai Xie, Hong-Lei Chen, Dian Wei, Bang-Yi Wei, Zheng-Hu Li, Jian-Wu Zhang, Wei Yu, Bing Han
Summary: A novel distal radical rearrangement of alkoxyphosphine is developed for the first time and applied to the regioselective radical fluoroalkylphosphorylation of unactivated olefins. By employing a one-pot two-step reaction under CFL (compact fluorescence light) irradiation, a series of fluoroalkylphosphorylated alkyl iodides and alcohols are easily synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
T. Parker Maloney, Alexander F. Dohoda, Alec C. Zhu, Forrest E. Michael
Summary: In this study, we reported a convenient and transition metal-free intermolecular propargylic C-H amination of alkynes. The reaction showed high yields for terminal, silyl, and internal alkynes with a wide range of functional groups. The regioselectivity of amination was found to be influenced by substitution pattern and relatively remote heteroatomic substituents.
Article
Chemistry, Multidisciplinary
Yi Wu, Bing Xu, Guofeng Zhao, Zhangjin Pan, Zhan-Ming Zhang, Junliang Zhang
Summary: A highly enantioselective palladium-catalyzed intermolecular tandem Heck/Cacchi reaction was developed for the synthesis of a broad range of enantioenriched compounds bearing all-carbon quaternary stereocenters of interest in pharmaceutical research. This method features inherent atom- and step-economy, high functional group tolerance, mild conditions, broad structural diversity, and excellent enantioselectivities.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xiang Li, Pinhong Chen, Guosheng Liu
Summary: A palladium-catalyzed intermolecular alkynylcarbonylation of unactivated alkenes has been developed using ethynyl benziodoxolones as alkynylation reagents, providing efficient synthesis of beta-alkynylcarboxylic esters from simple alkenes. The reaction exhibits moderate to excellent regioselectivity and excellent functional group compatibility under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Zuxiao Zhang, Pinhong Chen, Guosheng Liu
Summary: Radical-involved transition metal catalysis enables new reactivities, and copper-catalyzed radical relay shows great potential in C(sp(3))-H functionalization. Significant progress has been made in asymmetric C-H functionalization through ligand design.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Xiang Li, Jianbo Jin, Pinhong Chen, Guosheng Liu
Summary: Researchers have developed a palladium-catalyzed remote oxidative halogenation reaction for alkenes, leading to the efficient synthesis of primary alkyl halides. This study provides a cost-effective method to obtain valuable chemicals from readily available and inexpensive internal alkenes or mixtures of alkene isomers.
Article
Chemistry, Multidisciplinary
Xintuo Yang, Xiang Li, Pinhong Chen, Guosheng Liu
Summary: A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. The (EtO)(2)MeSiH/BQ redox system is crucial for the highly selective and efficient hydrooxygenation, where alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced by silane. This method provides an efficient access to optically pure alcohol esters from easily available alkenes with excellent enantioselectivities and features a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Dunqi Wu, Wenzheng Fan, Lianqian Wu, Pinhong Chen, Guosheng Liu
Summary: In this report, a copper-catalyzed asymmetric atom transfer radical addition (ATRA) reaction was studied, resulting in the successful synthesis of chiral chlorinated compounds using specific reagents and chiral ligands.
Article
Chemistry, Multidisciplinary
Pin Xu, Wenzheng Fan, Pinhong Chen, Guosheng Liu
Summary: The first enantioselective radical trifluoromethylation of benzylic C-H bonds has been achieved using a cooperative photoredox and copper catalysis system. This method provides straightforward access to structurally diverse benzylic trifluoromethylation products with excellent enantioselectivities under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Wenzheng Fan, Xueyao Zhao, Yunshun Deng, Pinhong Chen, Fei Wang, Guosheng Liu
Summary: A highly efficient and sustainable method for enantioselective benzylic C-H cyanation has been reported by merging electrophoto-and copper catalysis. The novel catalytic system allows independent regulation of key steps to achieve high selectivity, suitable for enantioselective benzylic C-H cyanation of diverse alkylarenes and late-stage functionalization of bioactive molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xiang Li, Xintuo Yang, Pinhong Chen, Guosheng Liu
Summary: In this study, a remote hydro-oxygenation method of alkenes under palladium catalysis is reported, which efficiently yields linear alcohols from both terminal and internal alkenes. The use of a compatible SelectFluor/silane redox system plays a crucial role in achieving excellent chemo- and regioselectivities. The reaction exhibits a broad substrate scope and excellent functional group compatibility.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Liang Fu, Xin Chen, Wenzheng Fan, Pinhong Chen, Guosheng Liu
Summary: A novel asymmetric radical strategy for the straightforward synthesis of atropisomerically chiral vinyl arenes has been developed, proceeding through copper-catalyzed atroposelective cyanation/azidation of aryl-substituted vinyl radicals. The key to the success of the radical relay process is the atroposelective capture of highly reactive vinyl radicals with chiral L*Cu(II) cyanide or azide species. Furthermore, these axially chiral vinylarene products can be easily transformed into atropisomerically enriched amides and amines, enantiomerically enriched benzyl nitriles via an axis-to-center chirality transfer process, and an atropisomerically pure organocatalyst for the chemo-, diastereo-, and enantioselective (4 + 2) cyclization reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiaonan Li, Tilong Yang, Jiayuan Li, Xiang Li, Pinhong Chen, Zhenyang Lin, Guosheng Liu
Summary: Palladium-catalyzed remote 1,n-dioxygenation (n = 4) of internal alkenes using engineered pyridine-oxazoline (Pyox) ligands is reported. The reactions exhibit high regio- and enantioselectivity, and have a broad substrate scope, providing optically pure 1,n-diol acetates as key synthons for bioactive molecules. Experimental and theoretical studies reveal that the regioselectivity is controlled by the reactivity disparity of two allylic C-H bonds, with the first palladium migration step being the regioselectivity-determining step facilitated by modified phenyl-substituted Pyox ligands.
Article
Chemistry, Organic
Yiming You, Jiawen Hu, Tao Wu
Summary: Few studies have been conducted on aryl-substituted allenyl monofluorides due to concerns about their stability. In this study, we report a copper-catalyzed regioselective synthesis of these structures using inexpensive and accessible aryl boronic esters under mild conditions. The arylated allenyl monofluorides were stable enough to be isolated and easily converted to various other fluorine-containing compounds. Preliminary asymmetric attempts indicated that the reaction could proceed via a selective beta-fluorine elimination process.
Article
Chemistry, Organic
Changyu Shao, Chuanqi Hou, Pinhong Chen, Haihui Peng, Guosheng Liu
Summary: Here, the first enantioselective acetoxycarbonylation of internal (Z)-alkenes using a sterically hindered Quinox ligand is reported. The resulting acetoxyester products can be easily transformed into various biologically important molecules, with moderate to good yields and excellent enantioselectivities, as well as good functional group compatibility. The further transformation of these acetoxyesters into natural product analogues demonstrates the synthetic utility and application of this method.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yunshun Deng, Ronghua Lu, Pinhong Chen, Guosheng Liu
Summary: In this study, we achieved an enantioselective cyanation of propargylic C-H bonds through the combination of photoredox catalysis with a copper-catalyzed radical relay. The propargylic radical was generated by an intramolecular 1,5-HAT process. This reaction provides a straightforward approach to access optically pure propargyl nitrile compounds under mild conditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhongming Cheng, Tilong Yang, Can Li, Yunshun Deng, Fangjia Zhang, Pinhong Chen, Zhenyang Lin, Shengming Ma, Guosheng Liu
Summary: This study presents a copper-catalyzed radical relay strategy for the site-selective cyanation of sp(2) C-H bonds in allenes. The reactions show broad substrate scope and remarkable functional group compatibility under mild conditions. The site-selectivity is attributed to the unique pocket created by the Cu-bound nitrogen-centered radical and the crucial hydrogen bonding between the fluoride and the hydrogen atom. Late-stage functionalization of drug-like bioactive molecules containing an allene motif becomes feasible.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Pin Xu, Wenzheng Fan, Pinhong Chen, Guosheng Liu
Summary: The first enantioselective radical trifluoromethylation of benzylic C-H bonds has been established by a cooperative photoredox and copper catalysis system, providing straightforward access to structurally diverse benzylic trifluoromethylation products in good yields with excellent enantioselectivities under mild conditions. Merging the cooperative photoredox catalysis with copper catalysis is essential for the reaction, where the photoredox catalysis is used for the generation of benzylic radicals from alkyl arenes through a hydrogen atom transfer process and the copper catalysis is used for the enantioselective trifluoromethylation of the benzylic radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
