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
John M. Halford-McGuff, David B. Cordes, Allan J. B. Watson
Summary: A Rh-catalyzed [2+2+2] cycloaddition approach for the synthesis of BMIDA-functionalized arenes is developed to address the reactivity issues associated with internal alkynes. The method enables the access to highly functionalized borylated benzene scaffolds, and exhibits broad functional group compatibility and high yields. The utility of the products is demonstrated through their elaboration and synthesis of fused heterocycles via intramolecular Chan-Lam etherification and amination. The dominance of sterically controlled reactivity is described.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Tian Feng, Jin-Xiu Ren, Xing Gao, Qiao-Qiao Min, Xingang Zhang
Summary: We developed a new practical and stable difluoroalkylating reagent that can introduce the difluoromethylene group into organic molecules under mild reaction conditions via copper catalysis. The method exhibits high selectivity and efficiency and can be used for the synthesis of various complex analogs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Tao Dong, Yibin Ye, Yanhui Wang, Kelvin Pak Shing Cheung, Gavin Chit Tsui
Summary: Under typical copper-catalyzed hydroboration conditions, ss(trifluoromethyl)styrenes undergo protodefluorination to form difluoromethylated alkenes, which is distinct from trifluoromethyl alkenes with alkyl substituents that predominantly give defluoroborylation products.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Maude Aelterman, Tony Biremond, Philippe Jubault, Thomas Poisson
Summary: The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed in this study. By adding electrogenerated boryl or silyl radicals onto various alpha-trifluoromethyl or alpha-difluoromethylstyrenes, a wide range of gem-difluoro and gamma-fluoroallyl boronates and silanes were successfully synthesized. The reactions were also scaled up under continuous flow conditions, demonstrating promising volumetric productivity. The synthetic utility of these building blocks was further highlighted through versatile transformations, and plausible reaction mechanisms were proposed to explain the formation of the products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Li-Cai Liu, Jiasheng Qian, Liyan Duan, Bin Wang, Fang-Hai Tu, Qingjiang Li, Honggen Wang
Summary: The facile synthesis of stereo-defined and transformable functionality-enriched building blocks is of great importance in modern organic chemistry, as it allows the rapid and divergent assembly of complex molecules. In this study, a halogen electrophile-initiated semipinacol rearrangement reaction of B(MIDA)-propargylic alcohols was reported, which leads to the synthesis of amphoteric alpha-haloalkenyl boronates with good yields and excellent stereoselectivities. The value of the products lies in their ability to undergo divergent conversions to polysubstituted alkenes through manipulation of the C-B and C-X (X=Br, I) bonds and the carbonyl group.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Ninglin Li, Fuqiang Xiong, Ke Gao
Summary: An efficient cobalt-based catalytic system has been developed for the protodeboronation of various aryl and vinyl boronates, tolerating a wide range of functional groups. Additionally, the reaction has been extended to deuterodeboronation with D2O, offering a potential protocol for the synthesis of regiospecifically deuterated arenes and olefins.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jie Shi, Li-Yun Guo, Qu-Ping Hu, Yu-Tao Liu, Qing Li, Fei Pan
Summary: A photoredox-catalyzed radical cascade reaction has been developed for the synthesis of lactam-substituted gem-difluoroalkenes, providing a simple method with good functional group tolerance and high yields.
Article
Chemistry, Multidisciplinary
Shichao Li, Muyao Li, Shu-Sen Li, Jianbo Wang
Summary: A palladium-catalyzed stereoselective synthesis method has been developed for obtaining trans-alkenyl MIDA boronates from N-Methyliminodiacetyl boronate (BMIDA)-substituted N-tosylhydrazone and benzyl bromides. The products show moderate yields and good functional group compatibility, with potential applications in the synthesis of other boron-containing compounds or in cross-coupling reactions.
CHEMICAL COMMUNICATIONS
(2022)
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
Lauriane C. Peyrical, Marie-Rose Ouellet-Du Berger, Maxim Boucher, Melodie Birepinte, Jean-Francois Paquin, Andre B. Charette
Summary: Trifluoromethyl (CF3) and pentafluorosulfanyl (SF5) substituted cyclopropane-fused gamma-lactones were successfully synthesized through Rh2(esp)2-catalyzed intramolecular cyclopropanation, with yields up to 99%. Twelve examples of this interesting scaffold are reported, along with postfunctionalizations to access highly functionalized CF3- and SF5- substituted cyclopropanes. These novel SF5-substituted analogues join the limited list of available pentafluorosulfanyl intermediates.
Article
Chemistry, Multidisciplinary
Benxiang Zhang, Jiayan He, Yi Li, Tao Song, Yewen Fang, Chaozhong Li
Summary: Acylphosphonates with the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton have been developed as efficient intermolecular radical acylation reagents for cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature. The protocol shows broad substrate scope and good functional group compatibility, providing satisfactory yields of branched ketones. The proposed mechanism involves Co-H mediated hydrogen atom transfer and subsequent trapping of alkyl radicals by acylphosphonates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yuyang Bai, Liping Cao, Siyuan Li, Guang'an Zhang, Yingguo Liu, Fengqian Zhao, Junliang Wu
Summary: A photoredox/Lewis acid cooperative catalytic system has been developed for the construction of C-vinyl-C-Rf bonds through the dehydrative difluoroalkylation of benzyl alcohols. Various allylic gem-difluorides were obtained with moderate yields and good to excellent E/Z selectivity. Control experiments were conducted and a possible mechanism for this process was proposed.
Article
Chemistry, Multidisciplinary
Shafrizal Rasyid Atriardi, Jae-Young Kim, Yulia Anita, Sang Kook Woo
Summary: In this study, a novel synthesis method for gem-difluoroalkenes was presented through visible-light photoredox-catalyzed defluoroaryloxymethylation of alpha-trifluoromethyl alkenes using alpha-sityl ethers as aryloxymethyl radical precursors. The reaction displayed good functional group tolerance and provided desired products with high yields. Mechanistic studies supported the proposal of a reaction mechanism involving single-electron oxidation of an alpha-silyl ether to generate an alpha-aryloxymethyl radical.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Xingchen Liu, Haohua Chen, Dali Yang, Binjing Hu, Ying Hu, Shengchun Wang, Yu Lan, Aiwen Lei, Jie Li
Summary: A multicomponent sulfonylation reaction using sulfonyl chlorides and OPiv-supported organozinc reagents was achieved via cobalt-catalyzed alkene difunctionalizations. Anion-coordination played a critical role in modifying the reactivity and chemical properties of organozinc reagents. The OPiv-coordination resulted in the lower reducibility of arylzinc pivalates, allowing for the in situ formation of catalytically relevant Co(I) species as the active catalyst in carbosulfonylation reactions.
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
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)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
