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
Chuntao Zhong, Huiling Tang, Benqiang Cui, Yanhui Shi, Changsheng Cao
Summary: This article describes a palladium-catalyzed Suzuki cross-coupling reaction of benzyl ammonium triflates via activation of a Csp(3)-N bond to construct a Csp(3)-Csp(2) bond. The reaction exhibits a wide substrate scope and functional group tolerance, and can be successfully performed in a one-pot process.
RESEARCH ON CHEMICAL INTERMEDIATES
(2022)
Article
Chemistry, Multidisciplinary
Liyan Fu, Jingwen You, Yasushi Nishihara
Summary: This method utilizes a palladium catalyst to synthesize unsymmetrical biaryls by cross-coupling acyl chlorides with potassium perfluorobenzoates under redox-neutral conditions. Compared to traditional methods, this synthetic strategy allows for the easy preparation of reactants from inexpensive aromatic carboxylic acids.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Anirban Mondal, Paco Visser, Anna M. Doze, Jeffrey Buter, Ben L. Feringa
Summary: Organolithium-based cross-coupling reactions are essential for constructing C-C bonds, especially for coupling various organolithium reagents with aromatic (pseudo) halides. The reaction can be completed within 10 minutes at room temperature and is compatible with organolithium-sensitive functional groups, showing potential applications in the synthesis of key intermediates for pharmaceuticals, chemical biology, and natural products.
CHEMICAL COMMUNICATIONS
(2021)
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
Di Qiu, Songyi Li, Guanglu Yue, Jinshan Mao, Bei Xu, Xinyu Yuan, Fei Ye
Summary: The desulfitative borylation reaction of sodium arylsulfinates with various diboron derivatives under palladium catalysis allows for the selective formation of C-B bonds to give arylboronates, demonstrating potential practical utility in organic synthesis.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Jian Luo, Bo Hu, Wenda Wu, Maowei Hu, T. Leo Liu
Summary: This study reports a redox neutral electrochemical C(sp(2))-C(sp(3)) cross-coupling reaction conducted under ambient conditions using nonprecious metal catalysts. The reaction demonstrated good yields and a broad scope, with potential applications in pharmaceuticals and natural amino acid modification. The method, which proceeds through an unconventional radical transmetalation mechanism, is highly productive and expected to have widespread applications in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Subhadra Ojha, Niranjan Panda
Summary: A novel Pd-catalyzed protocol for the desulfitative Heck-type reaction of N-methoxy aryl sulfonamides with alkenes was reported. The cross-coupling reaction was performed successfully with a variety of olefins to obtain aryl alkenes. Different substituents on the aromatic ring of N-methoxysulfonamides were also found to be compatible with the reaction conditions. The reaction proceeds through CuCl2-promoted generation of the nitrogen radical and subsequent desulfonylation under thermal conditions to afford the aryl radical for the Pd-catalyzed coupling reaction. N-Methoxysulfonamide was further exploited for the synthesis of symmetrical biaryls in the presence of CuCl2.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Tingting Yan, Kaki Raveendra Babu, Yong Wu, Yang Li, Yuhai Tang, Silong Xu
Summary: A phosphine-catalyzed olefinic cross-coupling reaction between benzyl halides and fumarates has been described, providing trisubstituted alkenes with good yields and excellent E-selectivity under metal-free conditions. Mechanistic studies suggest a catalytic cycle involving phosphorus ylide formation, Michael addition, water-assisted hydrogen transfer, and phosphine elimination.
Article
Chemistry, Multidisciplinary
Tamae Seo, Koji Kubota, Hajime Ito
Summary: Mechanochemical synthesis using transition-metal catalysts has advantages such as low solvent waste and short reaction times. However, the direct use of transition-metal catalysts in mechanochemical reactions without modifications limits the development of efficient cross-coupling processes. This study presents a new approach, using mechanochemistry-directed design to develop ligands for Suzuki-Miyaura cross-coupling reactions. The embedding of the ligand into a poly(ethylene glycol) polymer prevents catalyst deactivation and shows high catalytic activity at room temperature.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Haibo Zhu, Yingying Zhang, Gaowen Ren, Yaoqi Wang, Jia Meng, Qiangwen Fan, Zongbo Xie, Zhang-Gao Le
Summary: An efficient nickel-catalyzed cross-coupling reaction for the synthesis of 2-sulfonylthiazoles from readily available 2-chlorobenzothiazoles and sodium sulfinates has been developed. The reaction proceeds smoothly at room temperature, allowing for the successful coupling of diverse substitution patterns. The use of precious catalysts and sensitive ligands is avoided, resulting in moderate to excellent yields of various 2-sulfonylthiazoles.
CHEMICAL COMMUNICATIONS
(2023)
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, Applied
Maulik N. Mungalpara, Paul G. Plieger, Gareth J. Rowlands
Summary: The synthesis of pyridine-substituted [2.2]paracyclophanes using desulfinative cross-coupling has shown promising potential, addressing the challenges faced by traditional synthetic methods. This approach offers a solution for the preparation of these compounds and demonstrates the feasibility of utilizing pyridine sulfinates as coupling partners.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Nicholas E. Bode, Ryan T. McGuire, Mark Stradiotto
Summary: In this study, an effective catalyst system, PhPAd-DalPhos/NiCOD2, was identified and applied for the O-arylation of substituted phenols with chloropyridine-type electrophiles under thermal conditions, leading to pyridyl-O-aryl frameworks that are present in active pharmaceutical ingredients.
Article
Chemistry, Multidisciplinary
Sheng Zhang, Junchao Yin, Ziyang Wang, Yang Li, Yukang Fu, Ji Ma, Zhilong Xie, Ming Bao
Summary: A palladium-catalysed aromative benzylic allylation and allenylation of benzyl chlorides with allyl and allenyl pinacolborates is reported for the first time. The reactions are conducted smoothly in the presence of a bidentate phosphine ligand, yielding good cross-coupling products. This new synthetic method exhibits excellent tolerance for various functional groups and is compatible with sensitive groups such as NO2, CF3, CN, and COOMe. The utilization of a bidentate ligand and heating is crucial for the transformation. DFT calculation results reveal the importance of wide-bite-angle bidentate ligands for the formation of an eta(1)-benzyl-eta(1)-allylpalladium intermediate and the thermodynamic favorability of the normal coupling reaction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Fuhong Xiao, Minli Tang, Huawen Huang, Guo-Jun Deng
Summary: A metal-free method for the thiolation/aromatization of cyclohexanones with thiophenols to generate aryl sulfides has been developed, with oxygen serving as a green oxidant for the dehydroaromatic reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Cheng Li, Huawen Huang, Fuhong Xiao, Bin Zhao, Guo-Jun Deng
Summary: The study describes a practical strategy for skeletal diversification through combining selective C-H cleavage with C-C cleavage in a tandem reaction. Rhodium(iii)-catalyzed redox-neutral reaction of aryl oximes and internal alkynes generates novel N-(2-cyanoaryl) indanone imines with good yields, regioselectivities and atom economy, producing water as the only by-product. Experimental and theoretical studies offer mechanistic insights into this transformation, achieving an attractive integration of C-H activation with C-C activation in oxime transformation.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Minli Tang, Li Zhang, Guojiang Mao, Fuhong Xiao, Wen Shao, Guo-Jun Deng
Summary: A method for the synthesis of o-sulfanylanilines from cyclohexanones, amines, and thiophenols under transition-metal-free conditions is reported. This method involves the direct thioamination of cyclohexanones using N-iodosuccinimide (NIS) promoted oxidative dehydroaromatization. Non-aromatic cyclohexanones can be efficiently dehydrogenated and act as an aryl source using oxygen as an environmentally friendly oxidant. The resulting o-sulfanylanilines are demonstrated to be useful for the synthesis of N-arylphenothiazines.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Qiaoyan Xing, Fuhong Xiao, Guojiang Mao, Guo-Jun Deng
Summary: A simplified and efficient method for synthesizing thienopyrrolediones (TPDs) using simple starting materials under transition metal free conditions has been described. This method is environmentally friendly, atom-economic, and provides the basis for further development.
Article
Chemistry, Applied
Fuhong Xiao, Gang Yang, Lin Yao, Guojiang Mao, Guo-Jun Deng
Summary: A new strategy for the synthesis of target compounds from readily available starting materials has been developed using Fe-catalysis to carry out multiple-step reactions, achieving efficient synthesis of the target compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Gang Yang, Lin Yao, Guojiang Mao, Guo-Jun Deng, Fuhong Xiao
Summary: We have reported a metal-free protocol for the synthesis of indenoquinolinones and 2-substituted quinolines via [4 + 2] cycloaddition reaction using readily available 2-aminobenzaldehydes and ketones as starting materials. Different quinoline derivatives can be selectively synthesized by changing the type of ketones. O-2 and dimethyl sulfoxide (DMSO) as co-oxidants play an important role in the synthesis of indenoquinolinones. This condensation/oxidation strategy involves the formation of C-N, C-C, and C-O bonds, with the advantages of high yields and a broad substrate range.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Quanyuan Wang, Fuhong Xiao, Zhi Huang, Guojiang Mao, Guo-Jun Deng
Summary: In this study, a CuBr2-catalyzed annulation reaction of 2-bromo-N-arylbenzimidamide with selenium/sulfur powder was investigated, leading to the synthesis of benzo[d]isoselenazole and benzo[d]isothiazole products in good yields. This synthetic strategy exhibits broad substrate scope and functional group tolerance. Furthermore, the resulting products can be converted into N-aryl indoles via rhodiumIII-catalyzed ortho C-H activation of the N-phenyl ring, providing an efficient approach for the synthesis of axial aromatic molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shanping Chen, Zhuoqin Li, Kai Hu, Wei Feng, Guojiang Mao, Fuhong Xiao, Guo-Jun Deng
Summary: A three-component method using an iodine-containing reagent has been developed for the selective synthesis of phenothiazines and bis-phenothiazines. Starting from easily available cyclohexanones, elemental sulfur, and inorganic ammonium salts, this protocol selectively produces the desired compounds under aerobic conditions with satisfactory yields. This method offers a practical approach for the preparation of phenothiazines and bis-phenothiazines, utilizing readily available starting materials and metal-free conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Jiaxing Chen, Yongzhuo Xu, Wen Shao, Jianhua Ji, Boqiang Wang, Muyang Yang, Guojiang Mao, Fuhong Xiao, Guo-Jun Deng
Summary: A Pd-catalyzed C-O cross-coupling reaction was reported, which allows for the synthesis of highly congested hydroxylamines with an α-quaternary carbon center without cleavage of the N-O bond. This strategy shows high chemoselectivity, broad substrate scope, and excellent functional group tolerance, and has been demonstrated by pharmaceutical derivatization and postcatalytic modifications.
Article
Chemistry, Organic
Yanfeng Ma, Chunlan Zhou, Fuhong Xiao, Guojiang Mao, Guo-Jun Deng
Summary: A metal-free method for synthesizing 2-substituted quinolines and benzo[f]quinolines from aromatic amines, aldehydes, and tertiary amines has been developed. Cheap and readily available tertiary amines were used as the vinyl source, and a new pyridine ring was selectively formed through [4 + 2] condensation promoted by ammonium salt under neutral conditions and an oxygen atmosphere. This strategy offers a new route for preparing various quinoline derivatives with different substituents, allowing for further modifications.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yufeng Chen, Ruitong Yang, Fuhong Xiao, Tianci Xu, Guojiang Mao, Guo-Jun Deng
Summary: A three-component strategy using indole-2-carboxaldehydes, aromatic aldehydes, and ammonium acetate as starting materials was developed for the preparation of 3-phenyl-9H-imidazo-[1,5-a]-indol-9-one under copper catalysis conditions. This strategy involved the selective oxidation of the C3 position in the indole substrate into a ketone skeleton using oxygen as the sole oxidant and ammonium acetate as the nitrogen source, resulting in the formation of a new five-membered ring. Similar reaction conditions also allowed the synthesis of the same products from indole-2-carboxaldehydes and benzyl amines.
Article
Chemistry, Physical
Yufeng Chen, Ruitong Yang, Fuhong Xiao, Tong Li, Guojiang Mao, Guo-Jun Deng
Summary: A four-component synthesis of 2-phenyl-9H-pyrimido[4,5-b]indoles was successfully developed using indole-3-carboxaldehydes, aromatic aldehydes, and ammonium iodide as starting materials under transition-metal-free conditions. The pyrimidine ring formation and the formation of four C-N bonds were achieved in a one-pot reaction promoted by iodine and iodide additives. The use of two ammonium iodides as the sole nitrogen source is a notable highlight of this work.
Article
Chemistry, Organic
Yanfeng Ma, Tianci Xu, Fuhong Xiao, Guojiang Mao, Guo-Jun Deng
Summary: In this study, a metal-free multicomponent condensation sequence, [2 + 2 + 1 + 1], has been reported for the synthesis of polysubstituted pyridines. The starting materials are readily available and the reaction conditions are simple. This cyclization reaction exhibits good selectivity and yields various pyridines with a broad range of functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Dahan Wang, Li Zhang, Fuhong Xiao, Guojiang Mao, Guo-Jun Deng
Summary: An electrochemical method for achieving the C3-thiolation of quinoline compounds has been developed with maximum atom economy, direct conversion, and the use of simple and readily available starting materials. Various aryl/alkyl/heteroaryl thiols and even diselenides can undergo this transformation within the conditions of an undivided cell, providing C-S-bond-containing products in up to 84% yield. BF3 center dot OEt2 plays an irreplaceable role as an additive. Cyclic voltammetry and mechanistic studies suggest the interception of intermediates from the cathodic reduction of quinolines by thiols and disulfides.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Gang Yang, Lin Yao, Guojiang Mao, Guo-Jun Deng, Fuhong Xiao
Summary: A metal-free protocol for the synthesis of indenoquinolinones and 2-substituted quinolines using readily available 2-aminobenzaldehydes and ketones has been reported. Different quinoline derivatives can be selectively synthesized by altering the type of ketones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
