Article
Chemistry, Organic
Peng Dai, Yufei Li, Yu Chen, Jian Jiao, Qingqing Wang, Chenxiao Li, Yucheng Gu, Yanbin Zhang, Qing Xia, Wei-Hua Zhang
Summary: In this study, a facile and efficient approach to achieve monofluoromethylsulfinyl alkylation of quinoxalinones was developed, which involved the construction of new C-C and C-S bonds through the cleavage of C-F bond. The proposed mechanism was confirmed by density functional theory calculations, and the reaction exhibited a high level of atom economy. Moreover, the obtained products showed excellent biological activity.
Article
Chemistry, Organic
Yi Lu, Zhirui Liu, Chao Liu, Yunpeng Wu, Lu Li, Siyuan Liu, Hong Wang, Wei Gao, Zhenxian Liu, Jianbin Chen
Summary: An environmentally friendly electrochemical fluorotrifluoromethylation of styrenes was developed, which involves tandem processes of electro-oxidation and radical and nucleophilic addition. Using commercial CF3SO2Na and Et3N•3HF as the sources of CF3 and F, a range of potentially bio-active multi-site F-containing compounds were obtained in moderate to good yields. This catalyst- and oxidant-free fluorotrifluoromethylation strategy offers mild conditions and high step economy features, and the reaction mechanism was investigated using several analytical methods.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Yuta Ishikawa, Tatsuya Kameyama, Tsukasa Torimoto, Hajime Maeda, Masahito Segi, Taniyuki Furuyama
Summary: Phthalocyanine ruthenium complexes have been identified as red-light activatable catalysts for trifluoromethylation reactions, enabling the chlorotrifluoromethylation of alkenes without sacrificial reducing reagents. This reaction shows good compatibility with a blue-light-absorbing substrate, unlike traditional photoreaction conditions where the substrate decomposes completely under blue light irradiation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ling Yang, Dong-Hang Tan, Wen-Xin Fan, Xu-Ge Liu, Jia-Qiang Wu, Zhi-Shu Huang, Qingjiang Li, Honggen Wang
Summary: A new method was proposed utilizing benzyl N-methyliminodiacetyl (MIDA) boronates for photochemical radical C-H halogenation, enabling successful fluorination, chlorination, and bromination reactions. The resulting brominated product could be further transformed into a variety of organic compounds, including those difficult to form with alpha-halo sp(2)-B boronate esters, by reaction with different nucleophiles. An activation effect of the B(MIDA) moiety was discovered.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Jinfeng Huang, Yimin Jia, Xiangyu Li, Jianli Duan, Zhong-Xing Jiang, Zhigang Yang
Summary: A highly regioselective copper-catalyzed reaction has been developed for the first time to access tetrasubstituted allene derivatives containing halogen and CF3 groups with good to excellent yields. This practical and convenient method is compatible with a wide range of functional groups and has shown promising applications in the gram-scale preparation and late-stage functionalization of biologically active molecules.
Article
Chemistry, Multidisciplinary
Sachini Rodrigo, Atanu Hazra, Jyoti P. Mahajan, Hien M. Nguyen, Long Luo
Summary: AC electrolysis can overcome functional group compatibility limitations and enable sequential addition of two functional groups. Cyclic voltammetry studies indicate that product yields are influenced by the regeneration of starting materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jing Qi, Jinhui Xu, Hwee Ting Ang, Bingbing Wang, Nipun Kumar Gupta, Srinivas Reddy Dubbaka, Patrick O'Neill, Xianwen Mao, Yanwei Lum, Jie Wu
Summary: In this study, a novel electrophotochemical approach is presented for the selective trifluoromethylation of (hetero)-arenes using trifluoroacetic acid (TFA) as the CF3 source. The method offers sustainable and environmentally-friendly synthesis of CF3-, CF2H-, and perfluoroalkyl-containing (hetero)-arenes with improved chemoselectivity by light irradiation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xia Chen, Xiao-Yu Zhou, Hai-Long Liu, Sheng Zhang, Ming Bao
Summary: This paper describes an efficient and convenient method for the synthesis of 2-trifluoromethyl benzimidazoles. The cyclization reaction of various o-phenylenediamines with hexafluoroacetylacetone in the presence of Cu2O catalyst resulted in the formation of 2-trifluoromethyl benzimidazoles with high yields. Hexafluoroacetylacetone acted as both a cyclization partner and a ligand for the Cu catalyst, and various useful functional groups remained intact during the reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Pai Zheng, Chuan Liu, Qianding Zeng, Yi Zhang, Ying Liu, Jingjing He, Yupian Deng, Song Cao
Summary: A mild and practical Fe-catalyzed hydroxytrifluoromethylation of alpha-(trifluoromethyl)styrenes with CF3SO2Na in the presence of K2S2O8 and air has been developed. The reaction proceeds efficiently at room temperature without beta-fluoride elimination, resulting in good to excellent yields of alpha, beta-bistrifluoromethyl tertiary alcohols.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Meiyun Su, Lina Guo, Peiyu Mao, Meng Xiao, Wenjie Liu, Shaohua Wang
Summary: The catalyst-free electrochemical halogenation and trifluoromethylation of 4H-pyrido[1,2-a]pyrimidin-4-ones was successfully achieved under external-oxidant-free conditions. This strategy provides an easy and green approach for the synthesis of functionalized new 4H-pyrido[1,2-a]pyrimidin-4-one derivatives with broad scope, good functional group tolerance, and high regioselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shanshan Ma, Yawen Guo, Lidong Liu, Lin Shi, Xingyu Lei, Xinfang Duan, Peng Jiao
Summary: A mild and efficient coupling method for the reactions of gem-bromonitroalkanes with alpha,alpha-diaryl allyl alcohol trimethylsilyl ethers was reported. The coupling reactions were realized through a cascade involving visible light-induced generation of an alpha-nitroalkyl radical and a subsequent neophyl-type rearrangement. Structurally diverse alpha-aryl-gamma-nitro ketones, especially those bearing a nitrocyclobutyl structure, were prepared in moderate to high yields, which could be converted into spirocyclic nitrones and imines.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hao Jia, Andreas P. Haering, Florian Berger, Li Zhang, Tobias Ritter
Summary: In this study, we report the synthesis and application of a novel trifluoromethylating reagent TT-CF3+OTf-, which can be used in various trifluoromethylation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Energy & Fuels
Yuna Kim, Desiree Leistenschneider, Arno de Klerk, Weixing Chen
Summary: This study examined the potential of producing carbon fibers from asphaltenes, investigated the effects of various pretreatment methods on properties, and identified factors affecting melt spin productivity.
Review
Biochemistry & Molecular Biology
He-Ping Li, Xiang-Hong He, Cheng Peng, Jun-Long Li, Bo Han
Summary: This review summarizes the applications of late-stage functionalization strategies in the trifluoromethylation of natural products in the past ten years. These strategies include metal catalysis, organocatalysis, light-driven reactions, and electrochemical synthesis. The reaction models of each method are emphasized, along with the challenges, limitations, and future prospects of this approach.
NATURAL PRODUCT REPORTS
(2023)
Article
Chemistry, Organic
Kai Wang, Jiahao Hou, Yangjing Lv, Tingting Wei, Renren Bai, Yuanyuan Xie
Summary: An efficient electrolyte-triggered trifluoromethylation and halogenation at C5 position of 8-aminoquinoline derivatives was developed, giving moderate to excellent yields of C-H functionalization products. The mild and green reactions had lower energy consumption and shorter reaction times, while avoiding the use of transition-metal catalysts and oxidants.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yimiao He, Limei Tian, Xuexue Chang, Zeming Qu, Yanmin Huang, Chusheng Huang, Qing Sun, Honggen Wang
Summary: This article describes a rhodium-catalyzed reaction for the synthesis of fluorinated 2H-azepin-2-ones. The reaction is mild and efficient, with a broad substrate scope. The key steps for success are consecutive C-N bond formation and fluorine elimination.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Dong-Hang Tan, Zhi-Hao Chen, Ling Yang, Chang-Ting Li, Fang-Hai Tu, Qingjiang Li, Honggen Wang
Summary: A boryl-migratory semipinacol rearrangement of alpha-hydroxyallylboronates and alpha-hydroxypropargylboronates triggered by diverse halogen-, oxygen-, sulfur- and selenium-containing electrophiles was reported in this study. The method provides a mild and facile access to organoborons bearing valuable functionalities, with the sigma (C-B) hyperconjugation believed to be the key factor leading to the observed exclusive chemoselectivity and enhanced reactivity. The synthetic utilities of the formed products were demonstrated.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Wen-Xin Lv, Yin Li, Yuan-Hong Cai, Dong-Hang Tan, Zhan Li, Ji-Lin Li, Qingjiang Li, Honggen Wang
Summary: In this study, a hypervalent iodine-mediated oxidative gem-difluorination strategy was developed for the construction of gem-difluorinated alkylborons via an unusual 1,2-hydrogen migration event. The protocol showed high regio- and chemoselectivity and provided easy access to a broad range of beta-difluoroalkylborons under mild reaction conditions. The value of these products was demonstrated by transforming the boryl group into other valuable functional groups, offering a wide range of difluorine-containing molecules.
Article
Chemistry, Multidisciplinary
Jiasheng Qian, Zhi-Hao Chen, Yuan Liu, Yin Li, Qingjiang Li, Shi-Liang Huang, Honggen Wang
Summary: Allenylboronates are an intriguing class of organoborons that are challenging to synthesize and typically unstable, making separation difficult. This study presents a practical and concise route to a new class of stable and easily separable allenyl B(MIDA) through hydrazination/fragmentation of B(MIDA)-propargylic alcohols. The synthesis of optically active allenyl B(MIDA) was also achieved, and interesting reactivity of the resulting product was observed.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Medicinal
Xiao-Xuan Su, Yue-Ru Chen, Jia-Qiang Wu, Xiong-Zhi Wu, Kun-Tao Li, Xiao-Na Wang, Jia-Wei Sun, Honggen Wang, Tian-Miao Ou
Summary: Finding novel agents with anti-tumor activities is meaningful for non-small cell lung cancer (NSCLC) patients. Researchers designed and synthesized a series of carbazole derivatives and discovered that compound 5n showed notable activity in disrupting mitochondrial homeostasis and exhibited anti-tumor activity.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuan Liu, Zhi-Hao Chen, Yin Li, Jiasheng Qian, Qingjiang Li, Honggen Wang
Summary: This study reports a boryl-directed intermolecular C-H amination of internal alkenes, resulting in highly functionalized alpha-amino boronates with exceptional site-selectivity. The reaction conditions are mild, and the reaction is fully stereoretentive, allowing for further decorations on the unsaturated bonds within the product.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yin Li, Wen-Xin Fan, Shuang Luo, Alina Trofimova, Yuan Liu, Jiang-Hao Xue, Ling Yang, Qingjiang Li, Honggen Wang, Andrei K. Yudin
Summary: We report the observation and applications of the beta-boron effect that provides high regioselectivity in electrophilic addition reactions to allylic MIDA boronates. The boryl moiety is retained in the product, unlike the silyl group in the beta-silicon effect. Mechanistic studies reveal the role of sigma(C-B) hyper-conjugation in stabilizing the carbocation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Zhi-Hao Chen, Xiao-Xuan Su, Qingjiang Li, Jia-Qiang Wu, Tian-Miao Ou, Honggen Wang
Summary: A mild and metal-free synthesis of alpha-boryl ketones has been achieved via the hydration or oxidation of N-methyliminodiacetyl boronate (B(MIDA))-decorated alkynes. The hydration of arylethynyl B(MIDA)s can be conducted at room temperature with decent functional group tolerance using a new hydration system comprised of AcCl and H2O in HFIP. Furthermore, an oxidative carbon deletion process of propargylic B(MIDA)s has been developed for the synthesis of aliphatic alpha-boryl ketones, and an intriguing beta-boron effect has been observed to account for the unique site- and chemoselectivities. The application of the products in the synthesis of borylated heterocycles has also been demonstrated.
Article
Multidisciplinary Sciences
Jiang-Hao Xue, Yin Li, Dong-Hang Tan, Fang-Hai Tu, Yuan Liu, Qingjiang Li, Honggen Wang
Summary: A deaminative halogenation method for primary amines using N-anomeric amide as the nitrogen-deletion reagent is reported in this article. The method is suitable for direct halogenation reactions of both aliphatic and aromatic amines, and has been successfully applied to various complex and functional group-enriched bioactive compounds or drugs. Elaboration of the resulting products provides interesting analogues of drug molecules.
Article
Chemistry, Multidisciplinary
Shuang Yang, Jun-Yunzi Wu, Shuang Lin, Meicen Pu, Zhi-Shu Huang, Honggen Wang, Qingjiang Li
Summary: Divergent fluorination reactions of vinylcyclopropanes with different electrophiles are reported, allowing the facile synthesis of homoallylic monofluorides and vicinal-difluorides through ring-opening 1,5-hydrofluorination and ring-retaining 1,2-difluorination, respectively. Both protocols have mild conditions, simple operations, good functional group tolerance, and generally good yields. The practicality of these reactions is demonstrated by their scalability and the successful conversion of the formed homoallylic monofluorides into other complex fluorinated molecules.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Xu-Ge Liu, Qian Yang, Deng-Yin Liu, Jing Liu, Dong-Hang Tan, Yu-Jun Ruan, Peng-Fei Wang, Xiao-Li Wang, Honggen Wang
Summary: This study describes a nickel-catalyzed reductive decarboxylative/deaminative glycosylation of activated aliphatic acids/amines, resulting in efficient construction of various alkyl C-glycosides under simple and mild reaction conditions. The reactions exhibited high yields and broad substrate scope, enabling the transformation of some structurally complex natural products and late-stage modifications of drugs.
Review
Chemistry, Organic
Chen Zhihao, Fan Qi, Yin Biaolin, Li Qingjiang, Wang Honggen
Summary: Alpha-boryl carbonyl compounds have traditionally been considered thermodynamically unstable and prone to undergo 1,3-boron migration. In recent years, methods for synthesizing stable and separable alpha-boryl carbonyl compounds have been actively developed, thanks to the development and understanding of sp(3)-hybridized boron or tetra-coordinated boron. These methods include the insertion reaction of borane with diazo esters, sulfur ylides and other carbene precursors, the free-radical borylation reaction of alpha,beta-unsaturated carbonyl compounds, and late-stage structural modification reactions of boron-containing compounds. The recent advances in the synthesis of alpha-boryl carbonyl compounds are reviewed based on different reaction types, and the existing challenges and future research directions are discussed.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Yuan Liu, Shuang Lin, Yin Li, Jiang-Hao Xue, Qingjiang Li, Honggen Wang
Summary: This article reports a facile synthesis strategy for bicyclo[2.1.1]hexanes (BCHs) as bioisosteres of benzenoids in medicinal chemistry. The synthesis is achieved through a strain-release-driven [27r + 2o-] cycloaddition of bicyclo[1.1.0]butanes (BCBs) with alkenes using a pyridine-boryl radical catalyst. The mild reaction conditions, wide substrate scope, and good functional group tolerance make this protocol appealing for drug design and synthesis. Theoretical mechanistic studies suggest a radical relay mechanism, and synthetic applications of the products are demonstrated.
Article
Chemistry, Multidisciplinary
Shuwen Zhao, Xiaojia Cai, Yuying Lu, Jinhui Hu, Zhuang Xiong, Jingwei Jin, Yin Li, Honggen Wang, Jia-Qiang Wu
Summary: A mild, selective, and redox-neutral C-H activation/annulation reaction of salicylaldehydes with fluorovinyl tosylates is reported. The use of monofluorovinyl tosylate leads to the synthesis of C2- and C3-substitution-free chromones, while difluorovinyl tosylate results in the construction of C2-fluoroalkoxy chromones. The reaction exhibits mild conditions and good functional-group tolerance.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ling Yang, Yuan Liu, Wen-Xin Fan, Dong-Hang Tan, Qingjiang Li, Honggen Wang
Summary: This study presents a selenium-catalyzed regiocontrolled olefin transpositional chlorination and imidation reaction, where the use of an allylic B(MIDA) substitution improves the regioselectivity. The stabilization of alpha-anion from a hemilabile B(MIDA) moiety is believed to play a key role in the selectivity. The reaction shows broad substrate scope, good functional group tolerance, and generally good yields, making the formed products valuable precursors for the synthesis of structurally complex organoborons.
