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
Ziwei Luo, Yuwei Zong, Gavin Chit Tsui
Summary: The stereoselective C-F bond borylation of tetrasubstituted beta,beta-difluoroacrylates has been achieved using unsymmetrical diboron reagent (pin)B-B(dan) under the palladium(0)-catalyzed conditions. This method allows access to novel boronamides containing the monofluorinated vinyl-B(dan) functionality, which can directly cross-couple with gem-difluoroalkenes to afford vincinal difluoro 1,3-dienes with modular control of the substituents in Suzuki-Miyaura reactions.
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
Zhiwei Chen, Xiang Huang, Jian Liao, Min Wang
Summary: A copper-catalyzed enantioselective fluoroalkenylation of cyclic imino esters was developed, allowing for the synthesis of fluoroalkenylated products with good yields and broad substrate scope. Additionally, this method demonstrated high enantioselectivity in late-stage functionalization of pharmaceuticals.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Natsuki Oyama, Sota Akiyama, Koji Kubota, Tsuneo Imamoto, Hajime Ito
Summary: Asymmetric gamma-boryl substitution of trifluoromethyl- and silyl-substituted alkenes using a copper(I) salt and optically active C-1 symmetric QuinoxP*-type bisphosphine ligand as the catalyst has been successfully demonstrated. The resulting products, silyl-substituted gem-difluoroallylboronates and chiral silyl- and difluoromethylene-containing homoallylic alcohols, exhibit high enantioselectivity and can further be transformed into structurally complex fluorinated chiral molecules with the silyl groups serving as cross-coupling sites.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
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, Physical
Yanhui Wang, Xiaotian Qi, Qiao Ma, Peng Liu, Gavin Chit Tsui
Summary: The diastereoselective synthesis of densely functionalized tetrasubstituted (E)-monofluoroalkenes via Pd(0)-catalyzed base-free Suzuki-Miyaura crosscouplings offers a significant method for producing pharmaceutically relevant compounds. Computational studies support the reaction design, revealing an intriguing mechanism of C-F bond activation leading to complete control of stereoselectivity. This method does not require extraneous base assistance, making it a powerful tool for stereocontrolled synthesis of monofluoroalkenes.
Article
Chemistry, Organic
Matthieu Jouffroy, Philip Pye, Soufyan Jerhaoui, Wenyong Chen, Michel Surkyn
Summary: Researchers have discovered a highly selective MCL-1 inhibitor and improved the synthesis method to increase yield and decrease cost.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ziqi Zhu, Lin Lin, Jieshuai Xiao, Zhuangzhi Shi
Summary: The stereo- and enantioselective cross-electrophile coupling involving C-F bond activation was successfully achieved using a chiral nickel complex and B(2)pin(2) as a stoichiometric reductant. The reaction allows the construction of a C(sp(2))-C(sp(3)) bond under mild conditions, resulting in a variety of monofluoroalkenes bearing stereogenic allylic centers. Initial mechanistic studies suggest a radical chain pathway may be involved in the C-F bond activation process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Huaxin Lin, Wei Jiao, Zhiwei Chen, Jian Han, Dongmei Fang, Min Wang, Jian Liao
Summary: In this study, a new enantioselective Cu/ sulfoxide phosphine (SOP) complex catalyzed nucleophilic addition reaction was developed for the synthesis of chiral vicinal difluorides. The reaction showed high yields, Z/E-selectivity, and excellent enantioselectivities. This approach has great potential for the modification of complex biologically active compounds.
Article
Chemistry, Organic
Xinxin Han, Xin Liu, Christophe Len, Le Liu, Dongdong Wang, Yinbin Zhang, Xin-Hua Duan, Mingyou Hu
Summary: A switchable synthesis method is developed for the production of alcohols and ketones with a CF2-OR scaffold using visible-light promotion. The PDI catalysis method is characterized by its simplicity, broad substrate scopes, and the ability to switch between desired products without the need for transition metal catalysts. The presence or absence of a base is crucial in controlling the synthesis of the major desired products.
JOURNAL OF ORGANIC CHEMISTRY
(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.
Article
Chemistry, Organic
Shuai Liu, Yi-Sen Qian, Jian-Lin Xu, Lei Xu, Yun-He Xu
Summary: A three-component coupling method was reported for the regio- and stereoselective difunctionalization of allenes with allenyl ethers, bis(pinacolato)diboron, and gem-dichlorocyclobutenones as electrophiles, leading to highly functionalized cyclobutenone products tethering with an alkenylborate fragment. The polysubstituted cyclobutenone products also showed diverse transformation abilities.
Article
Chemistry, Organic
Xinyu Liu, Juanjuan Wu, Chun Zhang
Summary: A novel copper and palladium cocatalyzed defluorinative coupling of gem-difluoroalkenes and acyl chlorides has been developed. It is a practical method to prepare alpha-fluorochalcones, which are important units in various bioactive compounds. The reaction can smoothly generate desired products under mild conditions and the products can serve as versatile precursors to access complicated compounds. The proposed reaction mechanism is based on control experiments.
Article
Chemistry, Multidisciplinary
Yisa Xiao, Weichen Huang, Qilong Shen
Summary: A method for the stereoselective construction of Z-monofluoroalkenes by nickel-catalyzed defluorinative coupling of gem-difluoroalkenes in mild conditions was described. The combination of lithium organoborate and ZnBr2 generated in situ lithium aryl zincates, which facilitated the transmetalation step of the nickel-catalyzed cross-coupling reaction.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Xianghu Zhao, Chunmei Li, Biyun Wang, Song Cao
TETRAHEDRON LETTERS
(2019)
Article
Chemistry, Organic
Xuxue Zhang, Jingjing He, Song Cao
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Jingjing He, Kang Yang, Jianhong Zhao, Song Cao
Article
Agronomy
Xianghu Zhao, Chunmei Li, Jiuyong Xu, Xianfei Zhang, Hui Xiong, Qingchun Huang, Song Cao
Article
Engineering, Chemical
Chengyuan Xu, Yang Chen, Zhiyuan Zheng, Yongchun Liu, Song Cao, Yisheng Xu
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2020)
Article
Chemistry, Organic
Yisen Liu, Chunmei Li, Chuan Liu, Jingjing He, Xianghu Zhao, Song Cao
TETRAHEDRON LETTERS
(2020)
Article
Chemistry, Organic
Yupian Deng, Xuxue Zhang, Chuan Liu, Song Cao
Summary: The novel alkylation reaction of gem-dibromoalkenes with tertiary, secondary and primary alkyl Grignard reagents is highly dependent on reaction conditions and the type of Grignard reagents used. Specifically, efficient tertiary alkylation of gem-dibromoalkenes can be achieved in the presence of 50 mol% CuCN or under transition-metal-free conditions, leading to high yields of tertiary alkyl-substituted monobromoalkenes or alkenes.
Article
Chemistry, Organic
Sixue Xu, Yupian Deng, Jingjing He, Qanding Zeng, Chuan Liu, Yi Zhang, Bin Zhu, Song Cao
Summary: Four unprecedented base-catalyzed/mediated nucleophilic additions of TMSCN to alpha-(trifluoromethyl)styrenes and 2-trifluoromethyl enynes have been developed. The reaction proceeds smoothly at room temperature under mild and transition-metal-free conditions, affording the corresponding CF3-containing alkyl, alkynyl, and butadienyl nitriles in a highly regioselective manner with moderate to excellent yields.
Article
Chemistry, Multidisciplinary
Yupian Deng, Jingjing He, Song Cao, Xuhong Qian
Summary: Alpha-(trifluoromethyl)styrene and its derivatives are widely used in pharmaceuticals, agrochemicals, and advanced materials. They are versatile building blocks for the preparation of various compounds. Recent efforts have focused on developing reactions for accessing gem-difluoroalkenes and gem-difluoroalkylated compounds without defluorination. However, the use of alpha-(trifluoromethyl)styrenes in cycloaddition and hydroaddition reactions while retaining three C-F bonds remains underdeveloped.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Jingjing He, Chuan Liu, Yupian Deng, Qianding Zeng, Yi Zhang, Ying Liu, Pai Zheng, Song Cao
Summary: A mild and efficient DBN-mediated addition reaction was developed for the synthesis of various β-trifluoromethyl nitrogen-containing heterocycles and β-trifluoromethyl amines using α-(trifluoromethyl)styrenes and diazoles, triazoles, tetrazoles, and primary, secondary, and secondary cyclic amines.
Article
Chemistry, Organic
Zhihong Ma, Yupian Deng, Jingjing He, Song Cao
Summary: A highly efficient solvent-controlled synthesis of bis(trifluoromethyl)cyclopropanes and bis(trifluoromethyl)pyrazolines was developed. The reactions proceeded smoothly under transition-metal and base-free conditions, affording the expected products in good yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Xuxue Zhang, Chuan Liu, Yupian Deng, Song Cao
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Xianghu Zhao, Sixue Xu, Chuan Liu, Jingjing He, Chunmei Li, Yupian Deng, Song Cao
Article
Chemistry, Organic
Jialu Li, Chuan Liu, Jingjing He, Sixue Xu, Xianghu Zhao, Yue Zhu, Song Cao
ORGANIC CHEMISTRY FRONTIERS
(2020)
Article
Chemistry, Organic
Xianghu Zhao, Sixue Xu, Jingjing He, Yao Zhou, Song Cao
ORGANIC CHEMISTRY FRONTIERS
(2019)
