Article
Chemistry, Organic
Guoxiang Zhang, Hui He, Xiaoxiao Chen, Shao-Fei Ni, Rong Zeng
Summary: Here, we demonstrate an efficient catalytic system for the intermolecular anti-Markovnikov hydrophosphinylation of olefins using disulfide as a photocatalyst and a hydrogen atom shuttle. This metal-free, base-free, and redox-neutral condition allows alkenes with diverse electronic properties to efficiently proceed with the anti-Markovnikov P-H addition. A plausible mechanism involving the hydrogen atom transfer process between ArS and P(O)-H is proposed.
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, Multidisciplinary
Guangwu Sun, Herui Liu, Xiu Wang, Wenbo Zhang, Wenjun Miao, Qinyu Luo, Bing Gao, Jinbo Hu
Summary: In this manuscript, a novel palladium-catalyzed coupling reaction between gem-difluoroalkenes and aryl boronic acids is reported, which yields bioactive indane-type ketones with an all-carbon alpha-quaternary center. The mechanism involves a water-induced defluorination and cross-coupling cascade pathway, supported by characterization and stoichiometric reactions of the key intermediates RCF2PdII. The use of vinyl difluoromethylene motif as an in situ carbonyl precursor is unprecedented in transition-metal-catalyzed coupling reactions, and it is expected to spark broad interest in ketone synthesis, fluoroalkene functionalization, and design of new synthetic protocols based on the unique reactivity of difluoroalkyl palladium(II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jun-Qi Zhang, Chunjiao Shen, Shihao Shuai, Ling Fang, Dandan Hu, Jiali Wang, Yu Zhou, Bukuo Ni, Hongjun Ren
Summary: A green and efficient approach for the difunctionalization of ynamides by merging the electrochemical and organoseleniumcatalyzed processes is described. This strategy features mild reaction conditions, broad functional group tolerance and high atom-economy, and requires no external chemical oxidant, providing a sustainable alternative for the synthesis of polysubstituted oxazoles.
Article
Chemistry, Multidisciplinary
Yin-Long Lai, Shao-Xi Yan, Sheng-Ling Zhang, Yu-Hong Huang, Ru-Xin Hu, Yang-Chong Chen, Jian-Min Luo, Jianxiao Li
Summary: A reliable and efficient palladium-catalyzed cascade cyclization/alkylation reaction of oxime ethers with unactivated alkenes is reported, yielding a variety of structurally diverse isoxazole derivatives in moderate to good yields with excellent functional group compatibility. Ionic liquid [Aeim]Br serves as an environmentally friendly solvent and an accelerating agent, providing excess bromine source to eliminate bromomethane from oxime ethers. Moreover, the use of chain-walking strategy enables rapid generation of molecular complexity from readily available starting materials in organic synthesis.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jianxiao Li, Chenjing Hong, Yanan Niu, Bowen Wang, Wenfang Xiong, Huanfeng Jiang
Summary: A novel and reliable palladium-catalyzed oxylallylation reaction was developed for the synthesis of gem-difluorinated isoxazole derivatives. This strategy enables the direct combination of isoxazole motifs and gem-difluoroalkene units, which is challenging to achieve through conventional synthetic methods. The reaction proceeded with high atom- and step-economy and excellent functional group compatibility, providing structurally diverse products in moderate to good yields.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jianxiao Li, Zidong Lin, Dan He, Wanqing Wu, Huanfeng Jiang
Summary: This study presents a novel and viable palladium-catalyzed sequential cyclization/functionalization of alkynone O-methyloximes with unactivated vinyl ethers under aerobic conditions. The structure of the products can be successfully controlled by varying the nature of the substituents of the vinyl ethers. This method offers a convenient and straightforward synthetic protocol for preparing structurally diverse compounds with promising applications in synthetic and pharmaceutical chemistry, even on a gram scale.
CHINESE JOURNAL OF CHEMISTRY
(2021)
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, Multidisciplinary
Peter McNeice, Marc-Andre Mueller, Jonathan Medlock, Werner Bonrath, Nils Rockstroh, Stephan Bartling, Henrik Lund, Kathrin Junge, Matthias Beller
Summary: A lead- and palladium-free alternative to the Lindlar catalyst has been developed for semi-hydrogenation of alkynes. The catalyst, silica-supported nickel nanoparticles modified by nitrogen-doped carbon, shows high selectivity even in the presence of easily reducible groups, making it attractive for various synthetic applications.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yao-Yao Liu, Yuan-Lu Qu, Yan-Shang Kang, Yue-Lu Zhu, Wei-Yin Sun, Yi Lu
Summary: In this study, a Rh-catalyzed consecutive C-H bond olefination/annulation/olefination cascade directed by sulfonamide and ester groups has been developed. Under mild conditions and with the assistance of 1-adamantane carboxylic acid, a seven-membered metallacycle including an ester group was preferred over a five-membered one including a sulfonamide group for the third C-H activation. The Rh catalyst exhibits high reactivity in this transformation, catalyzing a triple C-H activation process with a low catalyst loading at 50 degrees C. This method has applicability in constructing various pharmaceutical derivatives.
Article
Chemistry, Organic
Kolimi Sayyad Basha, Rengarajan Balamurugan
Summary: Gold-catalyzed intermolecular hydroarylation using arylboronic acid as the reactant was reported. This carboxylic acid-directed arylation showed high regioselectivity, leading to the formation of α-aryl acrylic acids at the less electrophilic carbon in good yields. This method provides a convenient route to NSAID precursors.
Article
Chemistry, Organic
Wenlong Ren, Mingzhou Wang, Jianqiong Guo, Jintao Zhou, Jianxiao Chu, Yuan Shi, Yian Shi
Summary: A regioselective Pd-catalyzed hydrocarboxylation of terminal olefins with HCOOH is described. A wide variety of branched carboxylic acids can be obtained easily under mild reaction conditions with high regioselectivities. The operation of the reaction is simple and does not require handling toxic CO. The ligand and LiCl play important roles in reaction reactivity and selectivity.
Article
Chemistry, Organic
Lu Lei, Pei-Sen Zou, Zhi-Xin Wang, Cui Liang, Cheng Hou, Dong-Liang Mo
Summary: A regioselective Heck reaction catalyzed by a P-containing palladacycle was described, which affords 2-aryl-2,5-dihydrofurans and 2-aryl-2,3-dihydrofurans in good yields from 2,3-dihydrofuran with diaryliodonium salts and aryl iodides, respectively. Mechanistic studies and DFT calculations revealed the chemoselectivity and regioselectivity-determining step of this reaction.
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.
