Article
Chemistry, Multidisciplinary
Biki Ghosh, Reena Balhara, Garima Jindal, Santanu Mukherjee
Summary: The first catalytic enantioselective Fischer indolization of prochiral diketones containing enantiotopic carbonyl groups is developed through dynamic kinetic resolution. Catalyzed by a combination of a spirocyclic chiral phosphoric acid and ZnCl2, this approach efficiently synthesizes cyclopenta[b]indole derivatives with an all-carbon quaternary stereocenter in good to excellent enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Xiaodong Ma, Guozhu Zhang
Summary: This study describes a copper-catalyzed, highly enantioselective alkyl and aryl/azolation of alkenes, where the use of a specific chiral ligand plays a crucial role in the success of the chemistry. Anionic tridentate ligands are employed to enhance the reducibility of copper complexes, facilitating the generation of alkyl/aryl radicals and providing good enantiocontrol in the azolation. The three-component coupling reactions have mild reaction conditions and can tolerate a broad range of functional groups, allowing for the straightforward introduction of valuable azole functionalities into complex molecular systems through direct C-H functionalization.
Article
Chemistry, Organic
Yue Dong, Xiang Meng, Giri Gnawali, Mengyang Chang, Wei Wang
Summary: A photoredox catalytic asymmetric method is developed to introduce both aliphatic and aromatic side chains and deuterium into chiral methyleneoxazolidinone simultaneously. The coupling of readily available boronic acids with the chiral auxiliary yields structurally diverse alpha-deuterated alpha-amino acid derivatives with high diastereoselectivity and deuteration.
Article
Chemistry, Physical
Shaofang Zhou, Kang Lv, Rui Fu, Changlei Zhu, Xiaoguang Bao
Summary: The study demonstrates the successful construction of aliphatic C-N bonds via nickel/photoredox dual catalysis, utilizing single electron transfer and photocatalyst-induced mechanisms. Synergistic experimental and computational studies propose a reaction pathway involving oxidative quenching of the photocatalyst and a potential Ni-catalyzed cycle for C(sp(3))-N bond formation.
Article
Chemistry, Multidisciplinary
Xin Zhang, Shuo Tong, Jieping Zhu, Mei-Xiang Wang
Summary: Under the catalysis of PdBr2 and a chiral phosphoramidite ligand, mono (2-bromoaroyl)-substituted calix[4]arene derivatives with upper-rim underwent an easy enantioselective desymmetrization reaction, yielding 9H-fluorene-embedded inherently chiral calixarenes with good yields and excellent enantioselectivities. The transannular dehydrogenative arene-arene coupling reaction most likely proceeded through oxidative addition of the C-aryl-Br bond to a ligated palladium catalyst, followed by a sequence of enantioselective 1,5-palladium migration and intramolecular C-H arylation. This new family of inherently chiral calixarenes has unique chiroptical properties due to their highly rigid structure induced by the 9H-fluorene segment.
Article
Chemistry, Organic
Wan-Ying Tang, Ling Chen, Ming Zheng, Le-Wu Zhan, Jing Hou, Bin-Dong Li
Summary: A photoinduced oxidative alkoxycarbonylation of alkenes has been successfully demonstrated with alkyl formates as radical sources, providing a variety of alpha,beta-unsaturated esters with good regioselectivity and E selectivity under ambient conditions.
Article
Chemistry, Multidisciplinary
Biki Ghosh, Mahesh Singh Harariya, Santanu Mukherjee
Summary: The desymmetrization approach enables the construction of centrally chiral unfunctionalized arenes from unsymmetrically substituted arene rings. This approach is based on a [4+2]-cycloaddition reaction and greatly simplifies the synthesis of chiral arenes with outstanding enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Pol Martinez-Balart, Balazs L. Toth, Alvaro Velasco-Rubio, Martin Fananas-Mastral
Summary: Here we report a photocatalytic methodology that enables the direct allylation of strong aliphatic C-H bonds with simple allylic chlorides. The method relies on the cooperative interaction of two metal catalysts, allowing for functionalization of a variety of chemical feedstocks and natural products under mild conditions in short reaction times.
Review
Chemistry, Multidisciplinary
Cheng-Long Ji, Xinyi Zhai, Qing-Yun Fang, Chengjian Zhu, Jie Han, Jin Xie
Summary: In recent years, the activation of unactivated alkyl chlorides through light-induced processes has become a promising field in radical chemistry, allowing for the easy construction of carbon-carbon and carbon-heteroatom bonds. Recent studies in medicinal chemistry show that their presence is associated with high success rates in clinical trials. This review summarizes the recent advances in the photoinduced activation of unactivated alkyl chlorides and discusses the underlying mechanistic aspects, aiming to inspire developments in organic chemistry, drug synthesis, materials science, and related disciplines.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Yang Gao, Sima Yazdani, Aaron Kendrick, Glen P. Junor, Taeho Kang, Douglas B. Grotjahn, Guy Bertrand, Rodolphe Jazzar, Keary M. Engle
Summary: In this study, a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes is described, facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. The reaction allows coupling of both alkyl- and aryl-substituted alkynes with a variety of boryl and silyl reagents with high alpha-selectivity. The versatile intermediates produced are scalable and can participate in various downstream transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhang-Long Yu, Yong-Feng Cheng, Ji-Ren Liu, Wu Yang, Dan-Tong Xu, Yu Tian, Jun-Qian Bian, Zhong-Liang Li, Li-Wen Fan, Cheng Luan, Ang Gao, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed enantioselective functionalization of acyl radicals has been achieved through Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling. This reaction shows broad substrate scope, allowing for the synthesis of enantioenriched esters with challenging acyclic tetrasubstituted carbon stereocenters. With subsequent transformations, this reaction provides a convenient strategy for the rapid preparation of chiral C3 building blocks, especially from glycerol, which is industrially relevant. Mechanistic studies support the proposed C-O bond coupling of acyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yichang Liu, Biyin Shi, Zhao Liu, Renfei Gao, Cunlong Huang, Hesham Alhumade, Shengchun Wang, Xiaotian Qi, Aiwen Lei
Summary: Electrochemical synthesis has rapidly developed in recent years, with the majority of reactions proceeding through a radical pathway. Understanding the properties of radical intermediates is crucial for mechanistic studies and developing new reactions. This study directly researched the formation and structure of sulfonamide N-centered radicals using the time-resolved EPR technique under electrochemical conditions, and successfully applied the results in the discovery of an unactivated C(sp(3))-H arylation reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Shang-Hai Yu, Tian-Jun Gong, Yao Fu
Summary: A cooperative Cu/Pd-catalysed borylallenylation of 2-trifluoromethyl-1,3-enynes with propargylic carbonates under mild reaction conditions was developed, providing facile and efficient access to conjugated bisallenes with a broad range of functional groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shi-Jiang He, Shuai Zhu, Sheng-Qi Qiu, Wei-Yi Ding, Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: This study discovered a novel type of axially chiral anthrone-derived skeleton by introducing axial chirality on symmetric anthrone skeletons through stereoselective condensation. The enantioenriched anthrones could be further transformed into dibenzo-fused seven-membered N-heterocycles with well-defined stereogenic center via Beckmann rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Deyun Qian, Srikrishna Bera, Xile Hu
Summary: A nickel-catalyzed hydroalkylation method has been developed to assemble a wide range of chiral alkyl amines with high regio- and enantioselectivity from enecarbamates and alkyl halides. The method is suitable for both nonactivated and activated alkyl halides, producing enantiomerically enriched amines with high functional group tolerance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiao-Long Su, Liu Ye, Ji-Jun Chen, Xiao-Dong Liu, Sheng-Peng Jiang, Fu-Li Wang, Lin Liu, Chang-Jiang Yang, Xiao-Yong Chang, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: The development of enantioconvergent cross-coupling of racemic alkyl halides with heteroarene C(sp(2))-H bonds has been achieved using a copper(I)/cinchona-alkaloid-derived N,N,P-ligand catalytic system, leading to high enantioselectivity of alpha-chiral alkylated heteroarenes, which show promise in drug discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Lin Liu, Kai-Xin Guo, Yu Tian, Chang-Jiang Yang, Qiang-Shuai Gu, Zhong-Liang Li, Liu Ye, Xin-Yuan Liu
Summary: The copper-catalyzed asymmetric cross-coupling of C(sp(3))-C(sp) bonds with terminal alkynes reported in this study shows high to excellent enantioselectivity. The rational design of chiral oxazoline-derived ligands is critical for success in tolerating oxidative conditions and inducing challenging enantiocontrol. This approach offers direct access to a variety of synthetically useful compounds and has great potential for the synthesis of enantioenriched medicinally relevant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Liwen Xing, Ji-Ren Liu, Xin Hong, Kendall N. Houk, Christine K. Luscombe
Summary: In this study, the mechanistic study of Pd/Ag cocatalyzed cross dehydrogenative coupling (CDC) polymerization reveals that the second chain extension cross-coupling is more efficient than the first cross-coupling, which goes against the Carothers equation. Kinetic analyses and DFT calculations provide insights into the reasons behind this phenomenon, which has implications for the synthesis of molecules where C-H bond activation may be the limiting factor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Ying-Qi Zhang, Yang-Bo Chen, Ji-Ren Liu, Shao-Qi Wu, Xin-Yang Fan, Zhi-Xin Zhang, Xin Hong, Long-Wu Ye
Summary: The use of chiral Bronsted acids in catalytic asymmetric synthesis enables the direct activation of alkynes, leading to the construction of valuable spirocyclic enones and 2H-pyrroles with high yields and excellent enantioselectivity. This activation mode is expected to be widely applicable in catalytic asymmetric reactions involving ynamides and related heteroatom-substituted alkynes.
Article
Chemistry, Organic
Na Wang, Li-Wen Fan, Jin Zhang, Qiang-Shuai Gu, Jin-Shun Lin, Guo-Qiang Chen, Xin-Yuan Liu, Peiyuan Yu
Summary: This study investigates the highly enantioselective intramolecular hydroamination reaction and uncovers its uncommon reaction mechanism. The reactivity of this reaction is primarily determined by the substituents on the internal carbon of the alkene, as well as the substituents on the terminal alkene carbons. The lower acidity of chiral phosphoric acids compared to chiral NTPAs results in a slower reaction.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Wu Yang, Lin Liu, Jiandong Guo, Shou-Guo Wang, Jia-Yong Zhang, Li-Wen Fan, Yu Tian, Li-Lei Wang, Cheng Luan, Zhong-Liang Li, Chuan He, Xiaotai Wang, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: In this study, a strategy for catalytic enantioselective hydroxylation of prochiral dihydrosilanes is described. The reaction provides Si-chiral silanols with high enantioselectivity and excellent functional group compatibility. Furthermore, the obtained products exhibit high structural diversity and can be further transformed using established synthetic schemes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng-Fei Wang, Jiao Yu, Kai-Xin Guo, Sheng-Peng Jiang, Ji-Jun Chen, Qiang-Shuai Gu, Ji-Ren Liu, Xin Hong, Zhong-Liang Li, Xin-Yuan Liu
Summary: In this study, a copper/chiral N,N,N-ligand catalytic system was developed for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters, providing enantiocontrol over highly reactive alkyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Fu-Li Wang, Chang-Jiang Yang, Ji-Ren Liu, Ning-Yuan Yang, Xiao-Yang Dong, Ruo-Qi Jiang, Xiao-Yong Chang, Zhong-Liang Li, Guo-Xiong Xu, Dai-Lei Yuan, Yu-Shuai Zhang, Qiang-Shuai Gu, Xin Hong, Xin-Yuan Liu
Summary: In contrast to the well-established enantioconvergent radical C(sp(3))-C cross-coupling, the coupling of tertiary electrophiles to forge all-carbon quaternary stereocentres remains unexplored. Here, we demonstrate a general copper-catalysed enantioconvergent C(sp(3))-C(sp) cross-coupling using rational design of chiral ligands. This protocol provides a practical platform for the construction of chiral carbon building blocks of interest in organic synthesis.
Article
Chemistry, Organic
Jun-Bin Tang, Jun-Qian Bian, Yu-Shuai Zhang, Yong-Feng Cheng, Han-Tao Wen, Zhang-Long Yu, Zhong-Liang Li, Qiang-Shuai Gu, Guo-Qiang Chen, Xin-Yuan Liu
Summary: A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes has been established, providing facile access to various stereo-defined trisubstituted alkenes in high yield under mild reaction conditions.
Article
Chemistry, Multidisciplinary
Xiao-Yang Dong, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: This article mainly introduces the research progress on enantioconvergent radical cross-coupling reactions. Compared with chiral nickel catalysts, the study of copper-catalyzed enantioconvergent radical cross-coupling is less explored, primarily due to the weak reducing capability of copper. In recent years, researchers have been dedicated to developing chiral ligands for copper-catalyzed enantioconvergent radical cross-coupling to address the issues of enantiocontrol and reaction initiation speed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xian-Yan Cheng, Yu-Feng Zhang, Jia-Huan Wang, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: This paper presents a copper-catalyzed enantioselective intermolecular radical 1,2-carboamination reaction using readily accessible alkyl halides and alkenes. The success of this method is attributed to the conceptual design of a counterion/highly sterically demanded ligand coeffect, which promotes the ligand exchange and formation of chiral C-N bonds. The reaction is versatile and delivers various chiral amine building blocks of interest in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yong-Feng Cheng, Zhang-Long Yu, Yu Tian, Ji-Ren Liu, Han-Tao Wen, Na-Chuan Jiang, Jun-Qian Bian, Guo-Xiong Xu, Dan-Tong Xu, Zhong-Liang Li, Qiang-Shuai Gu, Xin Hong, Xin-Yuan Liu
Summary: The transition-metal-catalysed cross-coupling reaction has been widely used to construct carbon-carbon/heteroatom bonds. However, the development of heteroatom-heteroatom cross-couplings has been challenging. In this study, a new strategy using single-electron reductive elimination under Cu catalysis was demonstrated for enantioselective S-O coupling. This reaction showed its synthetic potential in preparing chiral alcohols, utilizing biomass-derived feedstock glycerol, and catalytic 4,6-desymmetrization of inositol. These results highlight the potential of enantioselective radical heteroatomic cross-coupling as a general chiral heteroatom-heteroatom bond formation strategy.
Article
Chemistry, Multidisciplinary
Zhang-Long Yu, Yong-Feng Cheng, Ji-Ren Liu, Wu Yang, Dan-Tong Xu, Yu Tian, Jun-Qian Bian, Zhong-Liang Li, Li-Wen Fan, Cheng Luan, Ang Gao, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed enantioselective functionalization of acyl radicals has been achieved through Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling. This reaction shows broad substrate scope, allowing for the synthesis of enantioenriched esters with challenging acyclic tetrasubstituted carbon stereocenters. With subsequent transformations, this reaction provides a convenient strategy for the rapid preparation of chiral C3 building blocks, especially from glycerol, which is industrially relevant. Mechanistic studies support the proposed C-O bond coupling of acyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)