Article
Chemistry, Multidisciplinary
Sanghyup Seo, Donghyeon Kim, Hyunwoo Kim
Summary: The reductive cross-coupling of terminal alkenes and N-heterocyclic bromides was successfully demonstrated through ligand optimization of Pd and CuH catalysis. The optimized ligands for Pd and CuH catalysis, Briphos and DTB-DPPBz respectively, were further applied to gram-scale production of clathryimine B.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Yiyang Zhang, Hong Sun, Ying Chen, Yaocheng Shi, Lei Yu
Summary: In this paper, it was discovered that a polyaniline-supported tungsten catalyst could efficiently catalyze the alpha-H alkylation reaction of ketone with alcohol, producing only water as the byproduct. The reaction occurred under mild conditions, with a wide substrate scope, and demonstrated strong production capacity.
Article
Chemistry, Organic
Chengqiang Cao, Yi Yang, Xin Li, Yunxia Liu, Hui Liu, Zengdian Zhao, Lei Chen
Summary: The reaction, catalyzed by palladium, efficiently constructs two new bonds with high yields, while the alkene group is easily functionalized, leading to the formation of products with a unique structure that is difficult to synthesize.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Liangliang Song, Lingchao Cai, Lei Gong, Erik V. Van der Eycken
Summary: Copper-catalyzed enantioselective coupling reactions have been extensively studied for the rapid synthesis of chiral molecules. Despite progress in polar and radical mechanisms, the development of general and practical strategies for the regio-, enantio-, and diastereoselective assembly of stereogenic centers remains challenging. The integration of photocatalysis with asymmetric copper catalysis offers new reaction pathways and diverse chiral compounds, expanding the scope of radical chemistry. This review provides a summary of recent advances in photoinduced copper-catalyzed enantioselective coupling reactions, with a discussion on the mechanistic aspects.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Organic
Hidenori Matsuyama, Xuan Zhang, Masahiro Terada, Tienan Jin
Summary: A versatile method for synthesizing alkylidene fluorenes and their heteroarene derivatives has been successfully developed by using a Pd(II)-catalyzed direct C-H/C-H coupling of o-alkenyl biaryls. Under aerobic oxidation conditions, the use of Pd(OAc)2 catalyst produces alkylidene fluorenes with various functional groups and diverse polycyclic systems. These resulting products can be utilized as versatile synthetic building blocks for constructing structurally diverse polycyclic arenes and heteroarenes.
Article
Chemistry, Organic
Yang Li, Arshad Ali, Junchao Dong, Yu Zhang, Lili Shi, Qun Liu, Junkai Fu
Summary: Using a directing-group strategy, a copper-catalyzed diamination of unactivated alkenes efficiently generates symmetrical diamines with high diastereoselectivity using readily available dialkylamines as amino sources, while unsymmetrical diamines require a one-pot or two-step operation. These reactions are proposed to proceed through aziridinium intermediates.
Article
Chemistry, Organic
Xinmiao Huang, Ling Tang, Zhiyong Song, Shuangshuang Jiang, Xianmao Liu, Ming Ma, Bo Chen, Yuanhong Ma
Summary: A nickel catalysis system has been developed for the desulfonylative C(sp(2))-C(sp(2)) reductive cross-coupling reactions of aryl sulfone derivatives with aryl bromides to form diverse biaryl compounds. The isolated and confirmed Ar-Ni(II)-SO(2)CF3 complex with a phosphine ligand through oxidative addition of aryl sulfone to Ni(0) species provides solid evidence for understanding the C(Ar)-SO2 bond activation and reaction mechanism.
Article
Chemistry, Organic
Yiu-Wai Yeung, Chun-Ming Chan, Yu-Ting Chen, Marco Chan, Mingyu Luo, Xin Gao, Bingnan Du, Wing-Yiu Yu
Summary: We have developed a Cu-catalyzed cross-electrophilic coupling reaction for the synthesis of alpha-amino acid derivatives using alpha diazoesters and O-benzoyl hydroxylamines. Cu(OAc)2 is used as the catalyst and polymethylhydrosilane (PMHS) as the hydride reagent. The reaction demonstrates excellent functional group compatibilities. The formation of a Cuacetoacetate complex was confirmed by ESI-MS analysis, and radical trap experiments suggest the involvement of nitrogen-centered radicals as intermediates. This strategy provides a simple and cost-effective approach for the synthesis of alpha-amino acid derivatives.
Article
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Loic R. E. Pantaine, David C. Blakemore, Ian B. Moses, Neal W. Sach, Andre Shavnya, Michael C. Willis
Summary: Heteroaromatic sulfinates are effective nucleophilic reagents in Pd-0-catalyzed cross-coupling reactions with aryl halides. Base-activated, latent sulfinate reagents, such as beta-nitrile and beta-ester sulfones, have been introduced to address challenges in purifying and solubilizing metal sulfinate salts, as well as their tolerance to multi-step transformations. These latent sulfinate reagents have proven to be stable through multi-step substrate elaboration and amenable to scale-up processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jun Chen, Yu-Jie Liang, Peng-Zi Wang, Guo-Qing Li, Bin Zhang, Hao Qian, Xiao-Die Huan, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study presents a photoinduced copper-catalyzed cross-coupling reaction for the generation of allylic esters. The reaction proceeds at room temperature with high regio- and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Cang Cheng, Xiang Zuo, Dongdong Tu, Bin Wan, Yanghui Zhang
Summary: A method for the synthesis of enantiopure eight-membered nitrogen heterocycles has been developed through diastereoselective cross-coupling of 2-iodobiphenyls with 2-bromobenzylamines. The products provide a new type of chiral scaffold with easy modification and high configurative stability, which could be used in asymmetric synthesis. Palladacycles formed via the C-H activation of 2-iodobiphenyls act as the intermediates, offering a new strategy for synthesizing medium-sized ring compounds.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Pravin Kumar, Manmohan Kapur
Summary: A ruthenium-catalyzed method for the direct C-H formylmethylation of various arylisoxazoles using isoxazole ring as a directing group has been developed. Manipulation of reaction conditions leads to the formation of fused-anthranils. Vinylene carbonate serves as both a formylmethyl cation equivalent and an acetylene equivalent through decarboxylation. Control experiments were conducted to explore the possible mechanism. This method provides a convenient and efficient approach for the synthesis of formylmethyl isoxazoles and fused-anthranils.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Han Cao, Xuejing Liu, Fusheng Bie, Yijun Shi, Ying Han, Peng Yan, Michal Szostak, Chengwei Liu
Summary: This study presents a general and practical palladium-catalyzed intramolecular decarbonylative coupling of thioesters with excellent functional group tolerance and broad substrate scope, using commercially available, cheap, and practical Pd(OAc)(2) catalyst and phosphine ligands under base-free conditions. This versatile protocol is easily performed on a gram scale and applied in late-stage drug derivatization.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Inorganic & Nuclear
Archana Rajmane, Sanjay Jadhav, Arjun Kumbhar
Summary: Pd-catalyzed cross-coupling reactions are crucial in achieving valuable organic transformations, and recent developments have focused on phosphine-free ligands such as N-heterocyclic carbenes and amines, which offer broad scope and environmental friendliness.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Marco A. Lopez, Joshua A. Buss, Shannon S. Stahl
Summary: Site-selective chlorination of benzylic C-H bonds is achieved using a specific catalyst and oxidant, resulting in higher selectivity and compatibility with diverse alkyl arenes. Sequential benzylic C-H chlorination/nucleophilic substitution leads to coupling products with oxidatively sensitive partners.
