Review
Chemistry, Multidisciplinary
Jin-Bao Peng, Xin-Lian Liu, Lin Li, Xiao-Feng Wu
Summary: Carbonylation is a powerful method for the preparation of carbonylated compounds, and asymmetric carbonylation is a direct approach to constructing chiral compounds. This review summarizes recent achievements in palladium-catalyzed asymmetric carbonylation reactions.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Physical
Ida Ziccarelli, Raffaella Mancuso, Francesco Giacalone, Carla Calabrese, Valeria La Parola, Alex De Salvo, Nicola Della Ca', Michelangelo Gruttadauria, Bartolo Gabriele
Summary: This article reports the successful heterogenization of the classical PdI(4)(2-)carbonylation catalyst on multi-walled carbon nanotubes. The newly developed heterogeneous catalyst shows good activity and recyclability in the oxidative monoaminocarbonylation reaction, with limited metal contamination in the final organic compounds.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Fu-Peng Wu, Xiao-Feng Wu
Summary: Regioselective transformation is achieved in copper-catalyzed regiodivergent borocarbonylation of imines with alkyl iodides, with different ligands controlling the regioselectivity to produce either alpha-amino ketones or alpha-boryl amides selectively.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yangyang Weng, Jingping Qu, Yifeng Chen
Summary: This study demonstrates the palladium-catalyzed allylic carbonylative Negishi cross-coupling reaction using sterically bulky aromatic isocyanides as a CO surrogate, leading to β,γ-unsaturated ketones with high regioselectivity and stereoselectivity. The advantages of this method include mild reaction conditions and a wide substrate scope due to the utilization of Negishi reagents as carbon nucleophiles.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Guang-Yan Xing, Ya-Cheng Zhu, Deng-Yuan Li, Pei-Nian Liu
Summary: On-surface synthesis, a powerful tool for atomically precise fabrication of low-dimensional carbon nanomaterials, has greatly enriched fundamental science and technology. Achieving high selectivity of covalent coupling reactions remains challenging due to the complicated reactivity of organic groups and irreversibility of covalent bonds. Only a few on-surface covalent coupling reactions are frequently used, and this Perspective focuses on the development and synthetic applications of on-surface cross-coupling reactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Organic
Rongxiang Chen, Ruo-Ling Jia, Wenbo Li, Wei Zhao, Kai-Kai Wang, Zhan-Yong Wang, Xueji Ma, Wei Dai, Aili Sun
Summary: The CuI-catalyzed coupling reaction of benzofuran-3(2H)-ones with amines allows for the direct synthesis of alpha-ketoamides, involving C-O bond cleavage and C=O/C-N bond formation. Mechanistic studies suggest that this reaction may proceed through a free radical process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Haifeng Chen, Huifeng Yue, Chen Zhu, Magnus Rueping
Summary: This study describes a nickel-catalyzed three-component reductive carbonylation reaction for the synthesis of aryl-alkyl ketones. Ethyl chloroformate is used as a safe and readily available source of CO, providing an efficient and practical alternative. Experimental and mechanistic studies provide insight into the complexity and sequence of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Alasdair K. Cooper, Megan E. Greaves, William Donohoe, Paul M. Burton, Thomas O. Ronson, Alan R. Kennedy, David J. Nelson
Summary: A nickel/dppf catalyst system successfully achieved Suzuki-Miyaura cross-coupling reactions of certain chloropyridines and chloroquinolines but not others, due to differences in the reaction mechanism. Chloropyridines rapidly undergo oxidative addition to the catalyst, while alpha-halo-N-heterocycles form catalytically inactive dimeric nickel species.
Article
Chemistry, Inorganic & Nuclear
Hojat Veisi, Bikash Karmakar, Pourya Mohammadi, Taiebeh Tamoradi, Saba Hemmati, Zeinab Joshani
Summary: In this review article, the application of metal nanoparticle-supported multiwalled carbon nanotubes (MWCNTs) in C-C and C-X (X = N, O, S) coupling reactions is discussed. These composites exhibit excellent catalytic performance in the formation of C-C and C-heteroatom bonds and can be easily isolated and recycled. The review highlights the potential and advantages of surface-engineered carbon nanotubes in organic cross-coupling reactions.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Nina V. Kuchkina, Svetlana A. Sorokina, Alexey V. Bykov, Mikhail G. Sulman, Lyudmila M. Bronstein, Zinaida B. Shifrina
Summary: The use of PEGylated nanocomposite catalysts has successfully stabilized Pd2+ complexes and Pd nanoparticles, demonstrating excellent catalytic activity in copper-free Sonogashira and Heck cross-coupling reactions. The reactions exhibit high yields in green solvents with low palladium loading and allow for easy magnetic separation and reuse without significant decrease in catalytic activity.
Article
Chemistry, Physical
Fengqian Zhao, Patrizio Russo, Raffaella Mancuso, Bartolo Gabriele, Xiao-Feng Wu
Summary: A copper-catalyzed carbonylation of alkyl iodides with phenols is reported, yielding corresponding esters in good yields. Aliphatic alcohols are also suitable partners in this reaction.
JOURNAL OF CATALYSIS
(2022)
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)
Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Qian Pu, Mingming Huo, Guojuan Liang, Lijuan Bai, Genhui Chen, Hongjiao Li, Peng Xiang, Hui Zhou, Jing Zhou
Summary: Highly selective divergent oxidative dearomatization coupling reactions have been reported, where the chemoselectivity is controlled by catalysts and bases. Three different kinds of polycyclic cyclohexadienones are generated from the same reactants (41 examples, 85-99% yield). This method represents a novel copper- and palladium-catalyzed C-H oxidative dearomatization of phenolic derivatives.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Lukas Hoff, Simon D. Schnell, Andrea Tomio, Anthony Linden, Karl Gademann
Summary: A silver-mediated Pd-catalyzed cross-coupling method for 3-bromo-1,2,4,5-tetrazine with boronic acids was presented in this study. It was found that electronic modification of the dppf ligand played a crucial role in achieving good turnover. Using this fast method, a variety of alkyl-, heteroatom-, and halide-substituted aryl- and heteroaryl-tetrazines were successfully prepared, with yields up to 87%.
Article
Chemistry, Multidisciplinary
Siqi Wang, Jian-Shu Wang, Jun Ying, Xiao-Feng Wu
Summary: A novel Pd-catalyzed carbonylative cyclization reaction of alkene-tethered indoles with phenols or aryl-boronic acids is reported, providing a facile access to indolo[2,1-a]isoquinoline scaffolds. This method utilizes benzene-1,3,5-triyl triformate (TFBen) as a CO surrogate for incorporating a carbonyl group into the indolo[2,1-a]isoquinoline framework, affording various carbonyl-containing indolo[2,1-a]isoquinoline derivatives in good yields.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Ren-Rui Xu, Xiuyu Fang, Xinxin Qi, Xiao-Feng Wu
Summary: A general and straightforward strategy for the synthesis of thioester-substituted oxindoles via a palladium-catalyzed thiocarbonylative cyclization process has been developed. Thioester-substituted oxindoles were obtained in moderate to high yields using sulfonyl chlorides as the sulfur source. Both aryl and alkyl sulfonyl chlorides were well tolerated, and Mo(CO)(6) played a dual role as both a CO source and a reductant in this approach.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zuguang Yang, Jianhua Tang, Chen Li, Zhengkai Chen, Xiao-Feng Wu
Summary: A rhodium(iii)-catalyzed regioselective C2-alkenylation of indoles has been developed for the construction of alpha-CF3 substituted enamines. CF3-imidoyl sulfoxonium ylides (TFISYs) were used as alkenylating agents for the first time, allowing the assembly of a wide array of indolyl- and trifluoromethyl-decorated enamine derivatives in moderate to good yields.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Jian-Xing Xu, Yang Yuan, Xiao-Feng Wu
Summary: In this review, we summarized and discussed the major achievements in transitional metal-catalyzed carbonylative transformations of ethylene. Ethylene hydroformylation, hydroesterification, hydrocarboxylation, hydroaminocarbonylation, dicarbonylation, and multicomponent carbonylation reactions can produce various bulk compounds and fine chemicals, including propanol, alkyl propanoates, succinic diesters, and multifunctionalized C3 compounds.
COORDINATION CHEMISTRY REVIEWS
(2023)
Review
Chemistry, Inorganic & Nuclear
Qingqiang Tian, Xue Yin, Rongjing Sun, Xiao-Feng Wu, Yahui Li
Summary: This review summarizes the main contributions to carbonylative conversion under 1 atm of CO since 1983 and discusses the related literature, demonstrating the attractiveness of carbonylative reactions conducted at 1 atm of CO due to their avoidance of special equipment and risks associated with high-pressure reactions.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Organic
Siqi Wang, Shuwei Li, Liangcai Liu, Jun Ying, Xiao-Feng Wu
Summary: Amide-containing indolo-[2,1-a]isoquinoline scaffolds were synthesized by palladium-catalyzed carbonylative cyclization of alkene-tethered indoles with nitro-arenes. Using Mo(CO)6 as the CO source and reductant, and nitroarenes as the nitrogen source, this reaction yielded various amide-containing indolo[2,1-a]isoquinoline derivatives in good yields. Additionally, the late-stage modifications of bioactive molecules using this protocol were demonstrated.
Article
Chemistry, Multidisciplinary
Zhi-Peng Bao, Youcan Zhang, Le-Cheng Wang, Xiao-Feng Wu
Summary: A novel palladium-catalyzed difluoroalkylative carbonylative cyclization of unactivated alkenes and ethylene gas has been developed for the synthesis of alpha-carbonyl difluoro-modified glutarimides. This method was also applied to the synthesis of GeMigliptin, a medicine approved for the treatment of type 2 diabetes mellitus.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Fu-Peng Wu, Xing-Wei Gu, Hui-Qing Geng, Xiao-Feng Wu
Summary: An unprecedented and challenging defluorinative arylboration has been achieved using a copper catalyst. This method provides a flexible and facile approach to obtain a diverse range of products from polyfluoroarenes under mild reaction conditions. Furthermore, an enantioselective defluorinative arylboration was successfully realized by employing a chiral phosphine ligand, resulting in chiral products with unprecedented levels of enantioselectivity.
Article
Chemistry, Physical
Han-Jun Ai, Hui-Qing Geng, Xing-Wei Gu, Xiao-Feng Wu
Summary: In this article, a catalytic alkoxycarbonylation method for unactivated alkyl chlorides is reported, which utilizes a pincer manganese catalyst to overcome the difficulties in activating C(sp3)-Cl bonds. This method enables straightforward access to various esters. Mechanistic studies show that the alkyl chlorides are directly activated through oxidative addition reactions.
Editorial Material
Chemistry, Organic
Xiao-Feng Wu, Paul J. Dyson, Bruce A. Arndtsen
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Zuguang Yang, Pinyi Li, Zhengkai Chen, Xiao-Feng Wu
Summary: A rhodium(III)-catalyzed C-H activation/[4+1] annulation reaction has been developed for the synthesis of diverse trifluoroacetimidoyl-substituted 11H-isoindolo[2,1-a]indoles. The reaction cascade involves C-H imidoylmethylation, tautomerization, and AgOAc-mediated C-N bond formation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Sihao Ling, Yu Zhang, Zhengkai Chen, Xiao-Feng Wu
Summary: A heating-induced desulfuration annulation reaction has been achieved to provide a pathway for the synthesis of biologically important 5-trifluoromethylpyrroles, by reacting pyridinium 1,4-zwitterionic thiolates and CF3-substituted imidoyl sulfoxonium ylides through an unusual ((3+3)-1) pathway under metal-free conditions, with the extrusion of 4-methoxypyridine, sulfur, and DMSO.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Organic
An Da-Lie, Bao Zhi-Peng, Wu Xiao-Feng
Summary: The synthesis and transformation of fluorine-containing organic molecules is an important frontier topic in fluorine chemistry that has profound impacts on life science and material science. Among these, the carbonylative transformation of fluorocarbon-containing substrates is a recently developed carbonylation reaction that still faces many challenges. This review summarizes the progress on carbonylation reactions of fluorocarbon-containing substrates based on transition metal palladium, nickel, and copper catalysis, and discusses representative reactions in detail to understand their mechanisms.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xing-Wei Gu, Yan-Hua Zhao, Xiao-Feng Wu
Summary: Here, a novel methodology using aryl sulfonium salts as aryne precursors for [3 + 2] cycloaddition reactions with azides is described. The reaction, employing readily available arenes as feedstock, exhibits excellent atom economy, environmental friendliness, and high functional group tolerance. Furthermore, the outstanding performance in gram-scale reaction, deuterium labeling, and derivatization reactions suggests potential opportunities for large-scale production and other applications.
Article
Chemistry, Applied
Xing-Wei Gu, Youcan Zhang, Fengqian Zhao, Han-Jun Ai, Xiao-Feng Wu
Summary: The combination of charge-transfer complex and light irradiation provides a promising solution for sustainable chemistry. In this study, a phosphine-catalyzed visible light-induced alkoxycarbonylation reaction was developed, demonstrating high functional group tolerance and excellent chemoselectivity. Additionally, a five-component perfluoroalkylative carbonylation reaction was achieved, allowing the synthesis of β-perfluoroalkyl acyloxy esters from unactivated olefins and perfluoroalkyl iodides.
CHINESE JOURNAL OF CATALYSIS
(2023)