Article
Chemistry, Multidisciplinary
Arun D. Kulthe, Prathama S. Mainkar, Srirama Murthy Akondi
Summary: A metal-free, three-component trifluoromethylative alkenylation reaction using beta-nitrostyrenes with unactivated alkenes has been developed under visible light, providing a series of trifluoromethylated aromatic alkenes in good to excellent yields.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Xiaoyi Zhang, Shen Ning, Yi Li, Yanjiao Xiong, Xuesong Wu
Summary: A synergetic catalytic system utilizing organophotocatalyst 4CzIPN, thianthrene, and methanol was developed for visible-light-induced Giese reactions of various alkanes and alkenes. The use of alkoxy radicals as hydrogen atom transfer reagents allows the reaction to proceed under mild conditions, providing alkylated products in moderate to excellent yields without the need for strong oxidants and transition metal reagents. The success of this approach relies on the in situ thianthrenation of methanol by thianthrene radical cation, triggering the generation of methoxy radical.
Article
Chemistry, Organic
Rong-Bin Liang, Can-Ming Zhu, Pei-Qi Song, Lei-Min Zhao, Qing-Xiao Tong, Jian-Ji Zhong
Summary: A simple photoredox-neutral approach is reported for the synthesis of valuable vicinal S,O- and S,N-disubstituted molecules through the three-component thiohydroxylation, thioalkoxylation, and thioamination of vinylarenes.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Jitao Xu, Zhilong Li, Yumin Xu, Xiaomin Shu, Haohua Huo
Summary: This study presents an enantioselective benzylic C(sp(3))-H alkenylation of alkylarenes with vinyl bromides via photoinduced nickel catalysis, allowing for the stereodivergent synthesis of enantioenriched Z- and E-alkenes bearing aryl-substituted, allylic tertiary stereogenic centers. The tunable Z/E-selectivity is achieved by energy transfer catalysis with choice of the photocatalyst counteranion, showcasing simple starting materials, mild reaction conditions, broad substrate scope, divergent Z- and E-selectivities, and high enantioselectivities. Additionally, a formal asymmetric benzylic C(sp(3))-H alkylation can be achieved through a one-pot alkenylation/reduction sequence, providing a complementary strategy for stereochemical control in C(sp(3))-C(sp(3)) bond construction.
Review
Chemistry, Multidisciplinary
Huifeng Yue, Chen Zhu, Long Huang, Abhishek Dewanji, Magnus Rueping
Summary: Metallaphoto-catalysis is an efficient platform for constructing various chemical bonds, with the transformation of native functionalities such as C(sp(3))-H bonds into functional molecules being an attractive strategy in organic synthesis. The merging of two powerful methodologies, metallaphoto-catalyzed benzylic and allylic C(sp(3))-H bond functionalizations, offers general and mild approaches for diversifying alkylbenzenes and alkenes.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Chang-Ming You, Cheng Huang, Sheng Tang, Peng Xiao, Shengchun Wang, Zhenhong Wei, Aiwen Lei, Hu Cai
Summary: Direct N-allylation of azoles with hydrogen evolution has been achieved by the synergistic combination of organic photocatalysis and cobalt catalysis. This protocol eliminates the need for stoichiometric oxidants and prefunctionalization of alkenes, and produces hydrogen (H2) as a byproduct. The transformation highlights high step and atom economy, high efficiency, and broad functional group tolerance, opening up a pathway for valuable C-N bond formation in heterocyclic chemistry.
Article
Chemistry, Organic
Fang Wang, Jiaming Chen, Xiaoqi Jia, Dailin Zhuang, Zhenyang Wan, Lifang Ma, Ziyuan Li
Summary: A remote directing group-enabled radical relay strategy for benzylic direct C(sp3)-H alkoxylation with alcohols at room temperature is developed, which achieves satisfactory site-selectivity, chemoselectivity, and reaction scope under simple and mild conditions without the need for ligands or additives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Roman Kleinmans, Leon E. Will, J. Luca Schwarz, Frank Glorius
Summary: The study reports a new method for synthesizing valuable tertiary carboxylic acids by combining radical addition with rearrangement reactions under photocatalytic conditions, enabling rapid access to complex carboxylic compounds in a single step. This method also allows for the efficient synthesis of GABA analogs, a structural motif that was previously inaccessible in related transformations.
Article
Chemistry, Organic
Jibin Li, Zheng Liang, Yuzhi Ren, Jian Gao, Ding Du
Summary: A new class of functionalized gem-difluorocyclopropanes bearing acyl groups was synthesized via the N-heterocyclic carbene catalyzed difluorocyclopropanation of alkenes with aldehydes and CF2Br2. This reaction involves a cascade three-component radical relay/intramolecular cyclization process. The protocol features metal- and photocatalyst-free reaction conditions, readily accessible starting materials, good functional group tolerance, and easy scalability. Moreover, this strategy is appealing to pharmaceutical chemistry because it is potentially useful in constructing and modifying bioactive molecules via late-stage functionalization.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Mengqi Luo, Shibo Zhu, Chengcheng Shi, Yunlong Du, Chao Yang, Lin Guo, Wujiong Xia
Summary: We report a vinyl radical-mediated 1,5-hydrogen atom transfer (1,5-HAT) strategy for remote C(sp(3))-H functionalization reaction, including cyanation, oxidation, and etherification. This method efficiently constructs structurally diverse gamma-cyano, gamma-carbonyl, and gamma-oxygenated alkenes with excellent stereoselectivity.
Article
Multidisciplinary Sciences
Chia-Yu Huang, Jianbin Li, Chao-Jun Li
Summary: Hydrogen atom abstraction from C(sp(3))-H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs. The authors demonstrate a photo-induced and chemical oxidant-free cross-dehydrogenative coupling between alkanes and heteroarenes using catalytic chloride and cobalt catalyst, achieving successful couplings with satisfactory yields. The dual catalytic platform features the in situ engendered chlorine radical for alkyl radical generation and exploits the cobaloxime catalyst for catalytic turnover enabling hydrogen evolution.
NATURE COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Yu Zhang, Tong Zhang, Shoubhik Das
Summary: The functionalization of the benzylic C(sp(3))-H bond is a powerful tool in pre-clinical research for lead discovery. It enables site-selective modifications and total synthesis of complex molecules, providing valuable insights into the formation and application of new C-C, C-O, C-N, and C-X bonds.
Article
Chemistry, Organic
Girish Suresh Yedase, Avishek Kumar Jha, Veera Reddy Yatham
Summary: This study presents a novel method for the visible-light-mediated cross-coupling of unactivated alkyl iodides with aryl bromides, through synergistic halogen atom transfer (XAT) and nickel catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Meng-Yuan Dong, Chun-Yu Han, Dong-Sheng Li, Yang Hong, Fang Liu, Hong-Ping Deng
Summary: In this study, a mild and operationally simple approach for allylic C(sp(3))-H alkylation without oxidants was developed through the triplet synergistic merger of Brønsted base/cobalt/photoredox catalysis. This strategy enables the direct allylic C(sp(3))-H alkylation of various branched alpha-olefins with protic C(sp(3))-H feedstocks.
Article
Chemistry, Organic
Lei Liang, Ge Guo, Chen Li, Song-Lin Wang, Yue-Hui Wang, Hai-Ming Guo, Hong-Ying Niu
Summary: The study demonstrates Cu-catalyzed intermolecular alkynylation and allylation of unactivated C(sp(3))-H bonds with SOMO-philes via HAT, using N-fluoro-sulfonamide as a reagent, resulting in high yields, good regioselectivity, and functional-group compatibility. Late-stage functionalization of natural products and drug molecules is also shown in the research.
Article
Chemistry, Applied
Hui-Min Jiang, Qing Sun, Jin-Peng Jiang, Jing-Hao Qin, Xuan-Hui Ouyang, Ren-Jie Song
Summary: We have described a method for the dicarbofunctionalization of alkenes, which allows for the introduction of alkyl and electron-rich aryl groups across the C=C bond of styrenes. This is achieved under copper catalyst and oxidative conditions, resulting in the construction of C(sp(3))-C(sp(2))/C(sp(3))-C(sp(3)) bonds via dual C-H functionalization. The method enables the synthesis of 1,1-diarylalkanes, which are important scaffolds found in natural products and drug molecules, by grafting electron-rich aromatics such as indoles, pyrroles, and trisubstituted aromatics.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Ya-Fei Han, Yang Li, Xuan-Hui Ouyang, Ming Hu, Jing-Hao Qin, Ze Tan, Jin-Heng Li
Summary: A new metal-free electron donor-acceptor (EDA) complex photocatalysis strategy is developed for the alkylative [3 + 2] annulation of N-alkyl isoquinolin-2-ium salts with common alkynes. This method, utilizing the catalytic isoquinoline-based EDA complex, shows excellent site selectivity, tolerance of various functional groups, and uses aqueous media without expensive external photocatalysts and promotors. Mechanistic study suggests that the EDA complex is formed by the association of a catalytic isoquinoline with N-alkyl isoquinolin-2-ium salts.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Biochemistry & Molecular Biology
Hui-Min Jiang, Yi-Lin Zhao, Qing Sun, Xuan-Hui Ouyang, Jin-Heng Li
Summary: This article summarizes the importance of oximes and hydroxylamines as a class of skeletons, which not only widely exist in natural products and drug molecules, but also serve as synthons extensively used in industrial production. Due to the weak N-O sigma bonds of oximes and hydroxylamines, they can be easily transformed into other functional groups by N-O bond cleavage. Therefore, the synthesis of N-heterocycle using oximes and hydroxylamines as nitrogen sources has attracted wide attention.
Article
Chemistry, Organic
Yi-Lin Zhao, Yong Yao, Wan-Ting Li, Jing-Hao Qin, Qing Sun, Jin-Heng Li, Xuan-Hui Ouyang
Summary: A new copper-catalyzed three-component functionalization/transformation of styrenes using polyhaloalkanes and arenes is discovered. The polyhaloalkanes generate corresponding poylalkyl radicals which are then utilized in the copper-catalyzed alkene functionalization, leading to the construction of various alkene derivatives. This method tolerates a wide range of substrates and functional groups, enabling the synthesis of versatile heteroarene-containing gem-dihaloalkenes, which are important backbones in bioactive molecules.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Ya-Fei Han, Gui-Fen Lv, Yang Li, Li-Jun Wu, Xuan-Hui Ouyang, Jin-Heng Li
Summary: This article presents a new method for the production of (Z)-3-(silylmethylene)indolin-2-ones through a mild acryl transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines with CO and silanes. The use of an acryl transient chelating group leads to an unprecedented alkyne cis-silylrhodation followed by aminocarbonylation to assemble the desired products.
Article
Chemistry, Organic
Long-Jin Zhong, Gui-Fen Lv, Xuan-Hui Ouyang, Yang Li, Jin-Heng Li
Summary: This study reveals a novel copper-catalyzed remote benzylic C-H olefination of N-fluoroamides using a Cu-radical mechanism. The reaction combines the advantages of radical transformations and transition-metal catalysis, and utilizes a cooperative Cu and dinitrogen-based ligand catalytic system to achieve site-selectivity around the nitrogen atom.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Hui-Min Jiang, Jing-Hao Qin, Qing Sun, Dong Zhang, Jin-Peng Jiang, Xuan-Hui Ouyang, Ren-Jie Song, Jin-Heng Li
Summary: This article describes a copper-promoted reductive cross-coupling of nitroarenes with 4-alkyl-1,4-dihydropyridines to produce N-alkylbenzenamines. The reaction enables the construction of C(sp(3))-N bonds under oxidative conditions, providing an elegant platform for assembling N-alkylbenzenamines with good tolerance for sensitive functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Multidisciplinary
Shiqi Tong, Kewei Li, Xuanhui Ouyang, Renjie Song, Jinheng Li
Summary: The article summarizes recent advances in the radical-mediated decyanative alkylation reactions of cyano(hetero)arene via photo/electrochemistry, discussing the mechanisms involved in cleaving C(sp3)-H, C(sp2)-H, C-C or C-hetero bonds and forming new C-C bonds.
GREEN SYNTHESIS AND CATALYSIS
(2021)
