Review
Chemistry, Multidisciplinary
Qi Pan, Yuanyuan Ping, Wangqing Kong
Summary: The use of nickel catalysts in reductive cyclization/cross-coupling reactions allows the construction of valuable chiral heterocycles with quaternary stereocenters. This method offers advantages in building C(sp3)-C bonds, but limitations including low chemoselectivity and availability of organometallic nucleophiles restrict its application. This Account presents recent research on tuning the selectivity and cyclization mode of reductive cyclization/cross-couplings using nickel catalysts. It demonstrates the synthetic potential of this approach and the control of migratory aptitude through ligand modification and nickel oxidation state.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Multidisciplinary Sciences
Geun Seok Lee, Daeun Kim, Soon Hyeok Hong
Summary: The use of alkyl chlorides in Pd-catalyzed Mizoroki-Heck coupling reactions remains a challenging issue due to the high thermodynamic barrier of alkyl chloride activation and the propensity of alkylpalladium complexes to undergo undesired beta-hydride elimination. However, this study demonstrates that alkyl chlorides, including tertiary ones, can efficiently participate in Mizoroki-Heck cross-coupling reactions under mild conditions via photoinduced Pd catalysis, offering great potential for late-stage functionalizations and molecular complexity.
NATURE COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Takahito Kuribara, Masaya Nakajima, Tetsuhiro Nemoto
Summary: Ligand design plays a crucial role in enhancing the performance of light-enabled catalytic processes. In this study, the authors synthesized a visible-light-activated secondary phosphine oxide ligand and applied it to Pd-catalyzed radical cross-coupling reactions. Through molecular design aided by computational calculations, the ligand enables ligand-to-Pd(II) and Pd(0)-to-ligand single-electron transfer under visible-light irradiation, facilitating radical cross-coupling reactions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Kitty K. Asahara, Kei Muto, Junichiro Yamaguchi
Summary: A Pd-catalyzed denitrative intramolecular Mizoroki-Heck reaction of nitroarenes with alkenes has been developed, providing a convergent synthetic method for benzo-fused cyclic compounds.
Article
Chemistry, Applied
Xiaopeng Peng, Yang Yang, Bingling Luo, Shijun Wen, Peng Huang
Summary: A diverse set of fluorenes can be conveniently constructed starting from cyclic diaryliodoniums and terminal alkenes through Pd-catalyzed reactions. These reactions involve a conventional Mizoroki-Heck reaction and a reductive Heck reaction, with a general scope of alkenes leading to the synthesis of 29 fluorenes, expanding the structural diversity of fluorenes.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Shentong Xie, Yuqing Yin, Ya Wang, Jiannan Wang, Xiaoqian He, Ruopeng Bai, Renyi Shi
Summary: The electroreductive cross-electrophile coupling is a powerful, green, and efficient method for constructing challenging C-C bonds, which has attracted increasing attention from organic chemists. Most of the previous works focus on direct two-electrophile cross-coupling. In this work, a nickel-catalyzed three-electrophile electroreductive cross-electrophile coupling has been developed, offering a direct and convergent synthesis to target molecules from easily available and cheap substrates under mild conditions.
Article
Chemistry, Organic
Shimeng Li, Jie Zhang, Zuowei Xie
Summary: This work describes a general method for the efficient production of a class of cage B-centered carboranyl radicals, which are useful intermediates for the preparation of a family of cage B-(hetero)arylated o-carboranes.
Article
Chemistry, Organic
Ganesh Chandra Upreti, Tavinder Singh, Kirti Khanna, Anand Singh
Summary: This article describes the development of excited-state palladium-catalyzed alkylative cyclization of acrylamides and the alkylation of quinoxalinones. The highlights of this reactivity manifold include the use of various unactivated alkyl halides as alkyl radical precursors and a simple catalyst system. The reactions have a wide scope, occur under mild conditions, and provide excellent yields of products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Lantao Liu, Fangyuan Cheng, Chenxiang Meng, An-An Zhang, Mingliang Zhang, Kai Xu, Naoki Ishida, Masahiro Murakami
Summary: A Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates. This method provides a convenient approach to chiral 2,3-dihydrobenzofurans with excellent enantioselectivities, and has been applied in the concise synthesis of analogues of cannabinoid receptor 2 agonists.
Review
Chemistry, Multidisciplinary
You Wang, Yuli He, Shaolin Zhu
Summary: Migratory cross-coupling via metal migration is a significant process in academic and industrial fields, providing an attractive alternative for the synthesis of challenging structures. This Account outlines recent progress and developments in the field, including migration-functionalization modes, diverse functionalizations, and strategies for regio- and stereocontrol.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Xiaowei Li, Yuxiu Li, Wenlong Shan, Zemin Wang, Ruihua Liu, Zhong Zhang, Xiangqian Li, Dayong Shi
Summary: Here we report the development of a Ni-catalyzed defluorinative cross-electrophile coupling of gem-difluoroalkenes with alkenyl electrophiles, enabling the formation of C(sp(2))-C(sp(2)) bonds. The reaction exhibits broad functional group compatibility and excellent stereoselectivity, providing access to various monofluoro 1,3-dienes. Additionally, we demonstrate the synthetic transformations and applications of this reaction for the modification of complex compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Wei Liu, Yan He, Zhi-Yuan Liu, Yanlin Li, Yan Li, Bing-Bing Wu, Ruo-Xin Jin, Xi-Sheng Wang
Summary: The introduction of a trifluoromethyl group into sulfur-containing compounds significantly alters their biochemical properties. While there have been reports of accessing various alpha-functionalized trifluoroalkanes via C-C bond forming reductive coupling, C-X reductive coupling remains unexplored. In this study, a concise and efficient Ni-catalyzed reductive C-S coupling is reported, enabling the synthesis of a series of alpha-CF3 functionalized thioethers in good to excellent yields under mild conditions, with a broad substrate scope and excellent functional group compatibility. Furthermore, this protocol provides a new approach for subsequent trifluoromethylation modification of sulfur-containing organic structures.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Lin Zhu, Jie Huang, Fanling Meng, Ziyun Tan, Xiao Meng, Yang Xiao, Lanlan Zhang, Wenyi Li, Chao Wang
Summary: A NiH-catalyzed migratory and non-migratory gem-difluoroallylation reaction of alkenyl amines with trifluoromethyl alkenes has been developed. This reaction offers high selectivity and diversity for the synthesis of fluoro-containing amines, which is beneficial for drug discovery.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Polymer Science
Noriyuki Suzuki, Shun Koyama, Rina Koike, Nozomu Ebara, Rikito Arai, Yuko Takeoka, Masahiro Rikukawa, Fu-Yu Tsai
Summary: Thermoresponsive diblock copolymers were successfully synthesized and utilized in palladium-catalyzed coupling reactions in water. The study demonstrated higher efficiency in extraction for PDEAAm copolymers compared to PNIPAAm copolymers. Furthermore, aggregative precipitation of products in Sonogashira coupling reactions was observed, and washing the precipitate with water resulted in high purity products with good yields.
Article
Polymer Science
Ameneh Ahmadi, Tahereh Sedaghat, Roya Azadi
Summary: In this study, a Palladium-based magnetic nanocomposite was synthesized and utilized as a catalyst for Suzuki coupling and Heck-Mizoroki coupling reactions, demonstrating efficient catalytic activity and recyclability.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2021)
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Chemistry, Organic
Lian Yang, Cheng-Pan Zhang
Summary: The visible-light-irradiated reductive hydrodediazoniation method described in the study is a mild and simple approach that achieves good yields without the need for catalysts or additives. It is also suitable for deuterodediazoniation reactions and shows excellent functional group tolerance.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lian Yang, Cheng-Pan Zhang
Summary: The thermal and photochemical Balz-Schiemann reaction was revisited in commonly used solvents under catalyst and additive-free conditions. It was found that using low- or non-polar solvents could enhance the fluorination of aryldiazonium tetrafluoroborates, allowing for effective reactions at low temperatures or under visible-light irradiation. PhCl and hexane were identified as cost-effective and reliable solvents for these reactions, providing good to excellent yields of aryl fluorides.
Article
Chemistry, Organic
Yu Ma, Ze-Yu Tian, Shuang-Yang Zheng, Cheng-Pan Zhang
Summary: Cyclopropyldiphenylsulfonium salt has been successfully used as an efficient allylation reagent in copper-catalyzed reactions with amines, providing N-allylated products in good yields. The method shows good functional group tolerance and excellent chemoselectivity, and offers an interesting approach for the synthesis of N-allyl amines.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Organic
Ze-Yu Tian, Yu Ma, Cheng-Pan Zhang
Summary: The application of alkylsulfonium salts as alkyl-transfer reagents in organic synthesis has reemerged. They can readily alkylate various nucleophiles, alkenes, arenes, alkynes, organometallic reagents, etc., and offer convenience, high efficiency, readily accessible and structurally diversified alkylation reagents, good functional group tolerance, and a wide range of substrate types.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Long-Yu Ran, Xue Ding, Xue-Ping Yan, Cheng-Pan Zhang
Summary: This article describes the synthesis of alkyl fluorides and carbonates via divergent dehydroxyfluorination and carbonation of alcohols with trifluoromethyl trifluoromethanesulfonate (CF3SO2OCF3). Reactions with BTMG in THF yielded alkyl fluorides in good yields, while reactions of two different alcohols with Et3N in DCM formed asymmetric carbonates in moderate to excellent yields. CF3SO2OCF3 was shown to serve as either a F or a CO reagent in the reactions by changing the base, enabling the selective construction of alkyl fluorides and carbonates with high efficiency. Notably, the synthesis of fluorine-containing asymmetric carbonates, which are difficult to prepare by other methods, was comprehensively achieved by this method, demonstrating its significant application potential in both academia and industry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Zeng-Hui Lin, Yu-Fei Yao, Cheng-Pan Zhang
Summary: Deuteration of arylthianthren-S-ium triflates with CD3OD or CD3OD/CD3COCD3 in the presence of Cs2CO3 by palladium catalysis or photoirradiation allows for the convenient synthesis of deuterated arenes in good yields. The Pd-catalyzed reaction generally gives better yields than the photoinduced deuteration, but exceptions exist. These reactions highlight eco-friendly conditions, simplicity, inexpensive deuterium sources, good functional group tolerance, and a range of substrates. This protocol provides a high selectively formal aromatic C-H deuteration for efficient deuterium labeling of multifunctionalized arenes and drug molecules.
Article
Multidisciplinary Sciences
Jing-Yan Dong, Hao-Nan Wang, Yan-Qian Xie, Cheng-Pan Zhang
Summary: This study presents a copper-mediated trifluoromethyltelluration reaction of arylboronic acids with [Me4N][TeCF3], using air as an environmentally friendly oxidant. The reaction proceeds smoothly under mild conditions, providing the corresponding trifluoromethyltellurated products in good yields. This method offers a convenient access to various TeCF3-containing molecules.
Review
Chemistry, Multidisciplinary
Lei Liu, Yu-Cheng Gu, Cheng-Pan Zhang
Summary: This review summarizes the advances in the synthesis and typical applications of carbamoyl fluorides, fluoroformates, and their analogues since 1980. It focuses on the use of O/S/Se=CF2 species or their equivalents as fluorocarbonylation reagents for the direct construction of these compounds from parent heteroatom-nucleophiles.
Article
Chemistry, Organic
Lei Liu, Yu-Cheng Gu, Cheng-Pan Zhang
Summary: Visible-light-induced decarboxylative trifluoromethylselenolation of (hetero)aromatic carboxylic acids with [Me4N][SeCF3], oxidant, and catalysts leads to the synthesis of various (hetero)aryltrifluoromethyl selenoethers in good yields. The reaction proceeds via a radical process involving oxidative decarboxylation of the carboxylic acids using NFSI as the oxidant, [di-tBu-Mes-Acr-Ph][BF4] as the photocatalyst, and 1,1'-biphenyl as the cocatalyst. The presence of copper salts enhances the trifluoromethyl selenoethers formation through Cu-mediated cross-coupling reactions. This protocol offers advantages such as visible light irradiation, mild reaction conditions, good functional group tolerance, and applicability to drug molecules, overcoming the limitations of known trifluoromethylselenolation methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fei Li, Xue Han, Ziang Xu, Cheng-Pan Zhang
Summary: This study presents a visible-light-induced metal-free trifluoromethylselenolation reaction of aryl iodides and bromides with [Me4N][SeCF3]. The reaction was carried out at ambient temperature by utilizing a light-sensitive SeCF3 reagent. Mechanistically, EDA complexes between aryl halides and the -SeCF3 anion or the base could be formed and excited by light, leading to intracomplex single-electron transfer (SET) processes that generate aryl and center dot SeCF3 radicals as crucial intermediates, enabling a convenient and environmentally friendly approach to various aryl trifluoromethyl selenoethers.
Article
Chemistry, Multidisciplinary
Jing-Yan Dong, Hao-Nan Wang, Cheng-Pan Zhang
Summary: Metal-free trifluoromethyltellurolation of indoles was achieved using [Me4N][TeCF3] as a reagent in the presence of NIS, resulting in the synthesis of 3-TeCF3-substituted indole derivatives in high yields. The reaction displayed good functional group tolerance and proceeded smoothly under mild conditions. It is noteworthy that [Me4N][TeCF3] exhibited distinct reactivity compared to [Me4N][SeCF3] in indole systems.
Article
Chemistry, Multidisciplinary
Lei Liu, Yu-Cheng Gu, Cheng-Pan Zhang
Summary: The trifluoromethylselenolation of arenes through Pd-catalyzed C(sp(2))-H activation with the assistance of a directing group and an oxidant has been established for the first time. This reaction tolerates various directing groups and functional groups, allowing selective installation of a SeCF3 moiety onto the ortho positions of arenes. Mechanistic studies suggest that the CF3SeSeCF3 intermediate generated in situ from the oxidation of [Me4N][SeCF3] may be the actual SeCF3 reagent in the reaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ze-Yu Tian, Cheng-Pan Zhang
Summary: This study reported an efficient visible-light-induced cross-coupling reaction of arylsulfonium triflate with [Me4N][SeCF3] for the synthesis of various aryl trifluoromethyl selenoethers. The reaction exhibits operational simplicity, high efficiency, catalyst- and additive-free conditions, wide substrate scope, and good yields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Kai-Li Tan, Hao-Nan Wang, Tao Dong, Cheng-Pan Zhang
Summary: An efficient method for oxidative trifluoromethylselenolation/N-acylation of indoles with excellent regioselectivity and good functional group tolerance was developed. This one-pot procedure provides a convenient access to a new class of indole derivatives, representing the first trifluoromethylselanyl bifunctionalization of indoles with the nucleophilic [Me4N][SeCF3] reagent.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)