Article
Chemistry, Organic
Shangsheng Zhou, Yu Pu, Zhengli Liu, Xiaoming Zhang, Jiang Zhu, Zhang Feng
Summary: This study presents a novel iron-catalyzed reaction that efficiently converts unactivated gem-difluoroalkenes, gem-dichloroalkenes, and gem-dibromoalkenes into 1,2-bis(boryl)-alkanes with high selectivity and broad substrate applicability. Preliminary mechanistic studies suggest that double beta-F elimination plays a role in the catalytic cycle, with 1,1-diborylated alkenes potentially serving as intermediates in this iron-catalyzed 1,2-diborylation reaction.
Article
Chemistry, Organic
Koushik Patra, Mallu Kesava Reddy, Sumitava Mallik, Mahiuddin Baidya
Summary: The nucleophilic reactivity of alpha,alpha-difluorinated gem-diols has been utilized to selectively synthesize biologically relevant 1,4-dihydropyridines and 3,4-dihydro-2-pyridones adorned with the valuable gem-difluoromethylene motif. The method is scalable, high yielding, and compatible with a wide range of substrates and functional groups. Additionally, the synthesis of difluorinated oxa-azabicyclo [3.3.1] nonane frameworks has been demonstrated through product diversification.
Article
Chemistry, Organic
Jun-Qi Zhang, Jiayue Liu, Dandan Hu, Jinyu Song, Guorong Zhu, Hongjun Ren
Summary: A scalable cyanation method for the synthesis of (hetero)arylacetonitrile derivatives from gem-difluoroalkenes has been developed. This method offers mild reaction conditions, excellent yields, a wide range of applicable substrates, and tolerance to various functional groups. Notably, the use of aqueous ammonia as a nitrogen source eliminates the need for toxic cyanating reagents or metal catalysts, providing a green and alternative approach for the synthesis of arylacetonitriles.
Article
Chemistry, Organic
Kai Xu, Zhenli Xu, Mengzhen Zhang, Xiaoxiao Yan, Guoliang Mao, Tao Wang, Yangjie Wu, Lantao Liu
Summary: The efficient aerobic oxidative hydroxysulfurization reaction developed in this study allows for the production of alpha,alpha-difluoro-beta-hydroxysulfides from gem-difluoroalkenes and aryl or alkyl thiols, demonstrating high levels of chemoselectivity and regioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Yong Wang, Yuxuan Li, Lei Wang, Shengtao Ding, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: In this study, a new method for efficient construction of gem-diboryl compounds with hetero-substituted carbon centers was developed. This method involves the alpha-dihydroboration of heteroalkynes and is a practical and atom-economic alternative to the conventional multistep synthetic strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Dachang Bai, Yuanyuan Guo, Dandan Ma, Xiuli Guo, Hao Wu
Summary: In this paper, an efficient method for the synthesis of diversified alpha-difluoromethyl amines through copper-catalyzed hydroamination of gem-difluoroalkenes is reported. The reaction proceeds through Cu-H insertion to gem-difluoroalkenes and gives valuable alkyl-CF2H-containing compounds. The reaction shows broad substrate scope with readily available starting materials and commercial catalysis.
Review
Chemistry, Organic
Xiao-Juan Zhang, Ya-Min Cheng, Xiao-Wei Zhao, Zhong-Yan Cao, Xiao Xiao, Ying Xu
Summary: Driven by the demand for optically active fluoro-containing molecules, the field of fluorochemistry has emerged as a hot topic. Synthesis of both monofluoro- and gem-difluoroalkenes is highly sought after due to their importance in biologically active molecules and as handles for constructing other fluorinated molecules.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Multidisciplinary Sciences
Jingjing Zhang, Jin-Dong Yang, Jin-Pei Cheng
Summary: The diazaphospholene-catalyzed hydrodefluorination can selectively construct gem-difluoroalkenes and terminal monofluoroalkenes, showing good group compatibility and almost quantitative yields.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Andrew J. Intelli, Ryan T. Lee, Ryan A. Altman
Summary: The installation of fluorine and fluorinated functional groups into drug-like scaffolds can greatly affect the properties of compounds. However, current synthetic methods are limited in their ability to incorporate certain potentially useful fluorinated substructures, such as the α,α-difluorophosphine oxide. This study presents a new approach using peroxide-initiated hydrophosphinylation reactions to prepare a wide range of α,α-difluorophosphine oxides and functions, utilizing readily available reagents and green solvents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wen-Yan Xu, Yu-Jie Li, Tian-Jun Gong, Yao Fu
Summary: In this study, a Cu/Pd-catalyzed borodifluorovinylation reaction was used to synthesize conjugated gem-difluoroalkene scaffolds with good functional group compatibility, using alkynes, difluoroethylene bromide, and B2pin2 as chemical feedstock.
Article
Chemistry, Organic
Jian Qiu, Cece Wang, Lu Zhou, Yixian Lou, Kai Yang, Qiuling Song
Summary: In this study, an efficient protocol for the construction of gem-difluorohomoallylic boronates was developed through a nickel-catalyzed radical promoted defluoroalkylborylation reaction under mild conditions, using α-trifluoromethyl alkenes and α-haloboronates as substrates. This reaction demonstrated a broad substrate scope, good functional group tolerance, and diverse transformations.
Article
Chemistry, Multidisciplinary
Leiyang Lv, Huijun Qian, Yangyang Ma, Shiqing Huang, Xiaoyu Yan, Zhiping Li
Summary: This study presents a robust Pd/NHC ligand synergistic strategy that achieves exclusive alpha-regioselectivity in the C-F bond functionalization reaction. The method enables the efficient construction of branched mono-defluorinative alkylation products.
Article
Chemistry, Physical
Pan Gao, Liping Cui, Guodong Zhang, Feng Chen
Summary: A catalytic defluorosilylation method is developed, providing concise and modular synthetic routes for gem-difluoroallylsilanes. Trifluoromethylalkenes and silacarboxylic acids are used as easy-to-prepare and stable silyl radical precursors. This method utilizes photoredox catalysis and features a unique decarboxylation followed by defluorosilylation without extra hydrogen atom transfer catalysis, offering mild reaction conditions and a broad substrate scope applicable to diverse electron-rich and electron-poor groups.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Zhengyu Li, Yizhi Zhang, Yunxiao Zhang, Xingyi He, Xiao Shen
Summary: In this study, a method for the synthesis of highly functionalized monofluorocyclohexenes through photocatalyzed cascade cyclization reactions of readily available alpha,beta-unsaturated carbonyl compounds and gem-difluoroalkenes is reported. The reaction shows broad substrate scope and high diastereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Linzi Wen, Boao Li, Ziyan Zou, Naifu Zhou, Chengbo Sun, Pengju Feng, Hongsheng Li
Summary: In this study, a direct electrolysis protocol was demonstrated for the chemo- and regio-selective difluorination, azo-fluorination, and fluoro-alkoxylation of gem-difluorostyrenes under mild conditions. The reaction allowed for the selective synthesis of a distinct type of long-chain perfluoroalkyl aromatics involving Et3N3HF as the fluorine source with/without other nucleophiles. The reaction exhibited good functional group tolerance and was amenable to gram-scale synthesis. Moreover, an electrochemical reduction of the benzyl C-F bond was also achieved.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
You-Jie Yu, Feng-Lian Zhang, Jie Cheng, Jing-Hao Hei, Wei-Ting Deng, Yi-Feng Wang
Article
Chemistry, Multidisciplinary
Jing Qi, Feng-Lian Zhang, Ji-Kang Jin, Qiang Zhao, Bin Li, Lin-Xuan Liu, Yi-Feng Wang
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Multidisciplinary Sciences
You-Jie Yu, Feng-Lian Zhang, Tian-Yu Peng, Chang-Ling Wang, Jie Cheng, Chen Chen, Kendall N. Houk, Yi-Feng Wang
Summary: A general strategy for sequential carbon-fluorine (C-F) bond functionalizations of trifluoroacetamides and trifluoroacetates has been described, enabling the sequential generation of difluoro- and monofluoroalkyl radicals for diverse fluorinated products. The reaction mechanism and chemoselectivity were established through experimental and computational approaches.
Article
Multidisciplinary Sciences
Tian Ye, Feng-Lian Zhang, Hui-Min Xia, Xi Zhou, Zhi-Xiang Yu, Yi-Feng Wang
Summary: Radical cascade reactions are powerful tools for constructing structurally complex molecules. However, controlling the stereochemistry of acyclic radical intermediates remains challenging. In this study, the authors report a new strategy for stereoselective hydrogen atom transfer to acyclic carbon radicals using N-heterocyclic carbene-boryl radicals triggered cascades, enabling control of the stereochemistry.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tian-Yu Peng, Zhe-Yuan Xu, Feng-Lian Zhang, Bin Li, Wen-Ping Xu, Yao Fu, Yi-Feng Wang
Summary: A strategically distinct dehydroxylative alkylation reaction of alpha-hydroxy carboxylic acid derivatives with alkenes has been developed. The reaction involves the attack of a 4-dimethylaminopyridine (DMAP)-boryl radical to the carbonyl oxygen atom, followed by a spin center shift (SCS) to initiate C-O bond scission. The resulting alpha-carbonyl radicals then couple with a wide range of alkenes, leading to various alkylated products. This strategy allows for the efficient conversion of alpha-hydroxy amides and esters derived from biomass molecules and natural products into valuable compounds. Experimental and computational studies have confirmed the reaction mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qiang Zhao, Bin Li, Xi Zhou, Zhao Wang, Feng-Lian Zhang, Yuanming Li, Xiaoguo Zhou, Yao Fu, Yi-Feng Wang
Summary: This study presents a straightforward three-step reaction sequence for the construction of diversely substituted all-carbon quaternary centers in organic synthesis. By using readily accessible activated trichloromethyl groups as the carbon source and appropriate promoters, three alkyl chains can be introduced selectively by functionalizing the three C-Cl bonds. The findings provide insights into reaction mechanisms and demonstrate the utility of this strategy in drug molecule synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Tian-Yu Peng, Feng-Lian Zhang, Yi-Feng Wang
Summary: This article summarizes the research progress on boron-centered radicals over the past few decades, with a focus on NHC-boryl radical mediated radical borylation reactions and selective activation of inert carbon-heteroatom bonds. The study demonstrates the potential for developing more powerful and valuable synthetic applications of LBRs and the promising opportunities for discovering new reactions.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Organic
Tesfaye Tebeka Simur, Tian-Yu Peng, Yi-Feng Wang, Xiu-Wei Wu, Feng-Lian Zhang
Summary: A boryl radical-promoted dehydroxylative alkylation of 3-hydroxy-oxindole derivatives is achieved by adding 4-dimethylaminopyridine (DMAP)-boryl radical to the amide carbonyl oxygen atom, inducing a spin-center shift process and promoting C-O bond cleavage. The elimination of a hydroxide anion from a free hydroxy group is also accomplished. Capture of the generated carbon radical with alkenes leads to a variety of C-3 alkylated oxindoles. This method offers a simple operation and broad substrate scope.
Article
Chemistry, Organic
Tesfaye Tebeka Simur, Tian-Yu Peng, Yi-Feng Wang, Xiu-Wei Wu, Feng-Lian Zhang
Summary: A boryl radical-promoted dehydroxylative alkylation of 3-hydroxy-oxindole derivatives is reported. The reaction involves the addition of DMAP-boryl radical to the amide carbonyl oxygen atom, causing a spin-center shift process that promotes C-O bond cleavage. The elimination of a hydroxide anion from a free hydroxy group is also achieved. The resulting carbon radical reacts with alkenes to furnish various C-3 alkylated oxindoles. This method offers a simple operation and broad substrate scope.
Article
Chemistry, Multidisciplinary
Feng-Lian Zhang, Bin Li, K. N. Houk, Yi-Feng Wang
Summary: This Perspective provides an overview of the radical transformations involving the spin-center shift (SCS) mechanism, which is a fundamental process inorganic synthesis and biochemical transformations. Experimental, kinetic, and computational studies have been conducted over the past 20 years, leading to the development and application of a range of useful radical transformations based on the SCS processes in organic synthesis.
Article
Chemistry, Organic
Jing Meng, Hui-Min Xia, Ai-Qing Xu, Yi-Feng Wang, Zhijuan Wang, Feng-Lian Zhang
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Qiang Zhao, Ji-Kang Jin, Jie Wang, Feng-Lian Zhang, Yi-Feng Wang
Article
Chemistry, Multidisciplinary
Yun-Shuai Huang, Jie Wang, Wan-Xin Zheng, Feng-Lian Zhang, You-Jie Yu, Min Zheng, Xiaoguo Zhou, Yi-Feng Wang
CHEMICAL COMMUNICATIONS
(2019)
Article
Chemistry, Organic
Yuting Liu, Chang-Ling Wang, Hui-Min Xia, Zhijuan Wang, Yi-Feng Wang
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)
