Article
Chemistry, Multidisciplinary
Youcan Zhang, Hui-Qing Geng, Xiao-Feng Wu
Summary: Transition-metal-catalyzed multi-component carbonylation using palladium catalyst was employed for the synthesis of functionalized esters from a range of phenols and alcohols, utilizing inexpensive carbon monoxide and perfluoroalkyl halides. The process showed good functional group tolerance, chemoselectivity, and applicability to pharmaceutical and bio-active substrates, resulting in high yields of the target products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Olatunji S. Ojo, Alejandro Bugarin
Summary: The study presents a new one-pot synthesis method for styrene derivatives using readily available natural products, achieving regioselectivity without transition metals. The methodology has broad nucleophile scope, even accommodating sterically hindered nucleophiles.
Article
Chemistry, Physical
Jian-Shu Wang, Jiangjie Zhang, Siqi Wang, Jun Ying, Chuan-Ying Li, Xiao-Feng Wu
Summary: A novel palladium-catalyzed domino carbonylative cyclization has been developed for the rapid construction of functionalized heterocycles. The reaction proceeds smoothly with the consecutive formation of C-C and C-X bonds using benzene-1,3,5-triyl triformate as the CO source, yielding a variety of biologically relevant derivatives.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Applied
Raffaella Mancuso, Melania Lettieri, Ida Ziccarelli, Patrizio Russo, Antonio Palumbo Piccionello, Bartolo Gabriele
Summary: A catalytic carbonylative approach is presented for the multicomponent synthesis of benzothiophene derivatives, based on an S-cyclization-demethylation-alkoxycarbonylation-reduction sequence promoted by the PdI2/KI catalytic system under relatively mild conditions. Benzothiophene-2-acetic esters are obtained in moderate to good yields starting from variously substituted substrates in combination with different alcohols as external nucleophiles.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Robert Geitner, Andrei Gurinov, Tianbai Huang, Stephan Kupfer, Stefanie Graefe, Bert M. Weckhuysen
Summary: In this study, the mechanism of alkoxycarbonylation of alkenes using different surrogate molecules was unraveled using in situ nuclear magnetic resonance (NMR) spectroscopy. It was found that the reaction proceeds through the C-H activation of in situ generated methyl formate instead of carbon monoxide as previously hypothesized. A kinetic model involving all major intermediates was established based on quantitative NMR experiments for knowledge-driven optimization of the reaction. Additionally, a new reaction mechanism was proposed based on in situ observed Pd-hydride, Pd-formyl and Pd-acyl species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Jiangjie Zhang, Jun Ying, Xiao-Feng Wu
Summary: A novel palladium-catalyzed tandem cyclization and carbonylation reaction was developed for the synthesis of indeno[1,2-b]indol-10(5H)-one derivatives. The reaction proceeded smoothly with high yields using formic acid as the CO source. This method can also be applied for the modification of various bioactive molecules.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Lijun Shi, Mingshan Wen, Fuwei Li
Summary: The study reports a selective method for the synthesis of fused N-heterocycles through palladium-catalyzed tandem reactions, which successfully addresses the selectivity issue in the presence of incompatible step reactions and effectively prevents side reactions.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Lucia Veltri, Tommaso Prestia, Patrizio Russo, Catia Clementi, Paola Vitale, Fausto Ortica, Bartolo Gabriele
Summary: A new multicomponent catalytic approach for the synthesis of important fused imidazole bicyclic compounds was developed in this study. By carrying out sequential reactions under oxidative conditions, various N-heterocyclic propargylamine derivatives were successfully transformed into the target products, some of which exhibited promising luminescence properties.
Article
Chemistry, Organic
Mikhail A. Losev, Andrey S. Kozlov, Vladimir B. Kharitonov, Oleg I. Afanasyev, Fedor S. Kliuev, Ludmila A. Bulygina, Natalya S. Khrushcheva, Dmitry A. Loginov, Denis Chusov
Summary: A simple and selective method using carbon monoxide as a reducing agent was developed for the preparation of amides from nitroarenes and carboxylic acids. The protocol does not require non-gaseous additives, simplifying product isolation and saving reducible functional groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Mikhail A. Losev, Andrey S. Kozlov, Vladimir B. Kharitonov, Oleg I. Afanasyev, Fedor S. Kliuev, Ludmila A. Bulygina, Natalya S. Khrushcheva, Dmitry A. Loginov, Denis Chusov
Summary: A straightforward and selective method using carbon monoxide as a reductant was developed to prepare amides directly from nitroarenes and carboxylic acids. This protocol simplifies product isolation by not requiring any non-gaseous additives and preserves reducible functional groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hui-Yi Yang, Liang-Quan Lin, Na-Qi Li, Zhi-Hui Ren, Zheng-Hui Guan
Summary: In this study, we reported a novel palladium-catalyzed selective branched 3,4-hydroaminocarbonylation of 1,3-dienes to synthesize beta,gamma-unsaturated amides. This reaction utilizes readily available starting materials and tolerates a wide range of functional groups, providing an easy and effective approach to access diverse alpha-substituted beta,gamma-unsaturated amides. Mechanistic investigations suggest that the hydropalladation of dienes is irreversible and the insertion of CO into the allyl-Pd species is likely the rate-limiting step.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Huahua Liu, Yuping Xiong, Zhiyuan Chen
Summary: An efficient intramolecular Heck annulation reaction and trapping of the resulting cyclic alpha-oxindolylpalladium species by CO and NH-sulfoximine at room temperature has been demonstrated, providing excellent yields of 3,3-disubstituted beta-indoly sulfoximidoyl amides under very gentle reaction conditions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhi-Peng Bao, Xiao-Feng Wu
Summary: This article develops an efficient and convenient palladium-catalyzed carbonylation reaction for the synthesis of 2-cyano-N-acetamide and 2-cyanoacetate compounds. The reaction proceeds under mild conditions via a radical intermediate, suitable for late-stage functionalization. Gram-scale experiment was successfully performed with low catalyst loading, yielding the target product excellently. Additionally, this transformation can be carried out under atmospheric pressure and provides alternative routes to drug precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuya Hu, Rui Sang, Robby Vroemans, Guillaume Mollaert, Rauf Razzaq, Helfried Neumann, Henrik Junge, Robert Franke, Ralf Jackstell, Bert U. W. Maes, Matthias Beller
Summary: In this study, a straightforward and efficient method for the selective synthesis of diesters using palladium-catalyzed direct carbonylation of di- or polyols with readily available alkenes was presented. The use of a specific palladium catalyst with the built-in-base ligand L16 allowed for esterification of all alcohols and a high n/iso ratio. The synthesized diesters were evaluated as potential plasticizers in PVC films through the measurement of the glass transition temperature (T-g) using differential scanning calorimetry (DSC).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Raffaella Mancuso, Ida Ziccarelli, Mariangela Novello, Corrado Cuocci, Roberto Centore, Nicola Della Ca', Diego Olivieri, Carla Carfagna, Bartolo Gabriele
Summary: The reactivity of 2-alkynylbenzoic acids under Pdl(2)/KI-catalyzed oxidative alkoxycarbonylation conditions has been studied. The reaction selectively produces high value added compounds under specific conditions. The structures of the products were confirmed by XRD analysis.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Organic
Yufei Song, Guangming Wei, Zhaolin Quan, Zhengkai Chen, Xiao-Feng Wu
Summary: An expedient and efficient method for synthesizing structurally diverse carbonyl-bridged bisheterocycles has been developed via a palladium-catalyzed four-component carbonylative cyclization. The reaction proceeds through a cascade of intramolecular Heck reaction, carbonylation, nucleopalladation, and reductive elimination, forming up to five chemical bonds under mild conditions. Carbon monoxide plays a critical role in the reaction, and an in situ generated acylpalladium species triggers the subsequent intramolecular cyclization, providing access to functionalized bisheterocycles with high efficiency and selectivity.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Ren-Guan Miao, Weiqi Dai, Xinxin Qi, Xiao-Feng Wu
Summary: C-S bond formation is important in organic synthesis, material science, and medicinal chemistry. This study presents a nickel-catalyzed desulfonative cross-coupling reaction for the synthesis of unsymmetrical thioethers. Using readily available sulfonyl chlorides as both electrophiles and sulfur precursors, various asymmetric thioethers can be synthesized with good yields and functional group tolerance.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Applied
Yue Sun, Sihao Ling, Yubo Duan, Jingxian Li, Zhengkai Chen, Xiao-Feng Wu
Summary: A metal-free approach for constructing 5-trifluoromethyl-1,4-dihydro-1,2,4-triazines has been developed using base-mediated [3+3] cycloaddition. This protocol offers readily available starting materials, mild reaction conditions, a broad substrate scope, high efficiency, good synthetic prospect, and scalability.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Zhi-Peng Bao, Xiao-Feng Wu
Summary: This article develops an efficient and convenient palladium-catalyzed carbonylation reaction for the synthesis of 2-cyano-N-acetamide and 2-cyanoacetate compounds. The reaction proceeds under mild conditions via a radical intermediate, suitable for late-stage functionalization. Gram-scale experiment was successfully performed with low catalyst loading, yielding the target product excellently. Additionally, this transformation can be carried out under atmospheric pressure and provides alternative routes to drug precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hefei Yang, Zhi-Peng Bao, Le-Cheng Wang, Xiao-Feng Wu
Summary: In this study, a new inexpensive metal-catalyzed carbonylation reaction of carbenes was demonstrated, enabling the modification of organisms, drugs, and material molecules. Using copper salt as the catalyst, important malonates and related compounds were synthesized in high yields under mild reaction conditions.
Article
Chemistry, Organic
Zekai Shen, Yong-Wang Huo, Xinxin Qi, Xiao-Feng Wu
Summary: A palladium-catalyzed thiocarbonylation reaction using S-aryl thioformates as the thioester sources was developed for the synthesis of alpha,beta-unsaturated thioesters from vinyltriflates. The reaction proceeded smoothly at low temperature, providing a variety of alpha,beta-unsaturated thioesters in good yields with excellent functional group tolerance. This protocol offers mild reaction conditions, broad substrate scope, and avoids the use of toxic CO gas or odorousthiols, making it a valuable method for the synthesis of alpha,beta-unsaturated thioesters via thioester transfer process.
Article
Chemistry, Organic
Jiajun Zhang, Xiao-Feng Wu
Summary: The development of mild methodology for converting inert C-H bonds to value-added molecules has been an attractive research focus. In this study, versatile palladium-catalyzed carbonylative cross-coupling reactions were reported, which allowed the selective transformation of arenes via C(sp2)-H thianthrenation to produce desired diaryl ketones in good to excellent yields. Diaryl ketones have important applications in antitumor drugs, the agrochemical industry, and synthetic chemistry.
Article
Chemistry, Multidisciplinary
Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu
Summary: This paper reports a general method for the anti-Markovnikov hydroaminocarbonylation of unactivated alkenes under mild conditions, using copper catalysis in combination with hydroxylamine electrophile reagents and poly(methylhydrosiloxane) (PMHS) as a cheap and environmentally friendly hydride source. The reaction tolerates a variety of functional groups and efficiently converts unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity (and high enantioselectivities/diastereoselectivities). Additionally, with minimal modification of the reaction conditions, alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation to alkyl amides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan Zheng, Bing-Hong Teng, Youcan Zhang, Xiao-Feng Wu
Summary: In this study, a photo-induced metal-free carbonylation reaction of aryl bromides was developed. The reaction showed good reactivity with alcohol and amine nucleophiles, and a variety of useful aryl esters and amides were synthesized at room temperature in moderate to good yields.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Yang Yuan, Nai-Xian Sun, Chang-Sheng Wang, Kai Guo, Xiao-Feng Wu
Summary: We have developed an efficient method for synthesizing one-carbon-extended alcohols through cobalt-catalyzed hydroxymethylation of alkyl halides using carbon monoxide as the C1 source and cost-effective and environmentally friendly PMHS as the hydride source. This method includes a ligand-free cobalt catalyst and exhibits broad functional group tolerance.
Article
Chemistry, Organic
Xing-Feng Pan, Xuanzhang Bao, Ren-Rui Xu, Xinxin Qi, Xiao-Feng Wu
Summary: A straightforward and efficient method for the synthesis of carbamoyl-substituted oxindoles was developed using a palladium-catalyzed Heck cyclization and reductive aminocarbonylation reaction. This reaction demonstrated good compatibility with various functional groups, tolerating both nitroarenes and nitroalkanes. Employing Mo(CO)(6) as a solid CO source, a wide range of carbamoyl-substituted oxindoles were obtained in moderate to high yields without the need for external reductants.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jiajun Zhang, Le-Cheng Wang, Zhi-Peng Bao, Xiao-Feng Wu
Summary: A new reaction for site-selective carbonylation of arenes via C(sp(2))-H thianthrenation under mild conditions has been developed. High yields of desired 1,2-diarylethanones are obtained using low loadings of palladium catalysts. This strategy also allows for late-stage modification of complex molecules, which was previously challenging with similar carbonylative Negishi-type reactions.
Article
Chemistry, Organic
Yubo Duan, Shu-Ning Lu, Zuguang Yang, Zhengkai Chen, Xiao-Feng Wu
Summary: An efficient and straightforward strategy for the divergent synthesis of trifluoromethyl-substituted (dihydro)pyrimidoindolones via Rh(iii)-catalyzed C-H activation/annulation of N-carbamoylindoles with CF3-imidoyl sulfoxonium ylides has been achieved. The cascade reaction proceeds through a C-H imidoylmethylation, tautomerization and intramolecular nucleophilic addition sequence, leading to the construction of a wide range of functionalized pyrimidoindolone derivatives in good to excellent yields under redox-neutral conditions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Han -Jun Ai, Fengqian Zhao, Xiao-Feng Wu
Summary: Iron-catalyzed carbonylation reactions are highly desirable due to their low cost, abundance, and distinct reactivity patterns. In this study, we developed a method for the carbonylative coupling of unactivated alkyl halides with amines, amides, and indoles, resulting in the synthesis of various amides, imides, and N-acyl indoles with high yields and compatibility with other functional groups. Our mechanistic studies revealed that the reaction pathway depends on the substrate, with alkyl iodides proceeding via a radical pathway and alkyl bromides undergoing a two-electron transfer process.
CHINESE JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Hui-Qing Geng, Xiao-Feng Wu
Summary: Cyclopropane is a crucial ring found in various bioactive compounds, especially in clinical medicines. It can be synthesized by reacting olefins with potentially hazardous diazo-derived carbenoids. Carbonylation is a powerful tool for synthesizing carbonylated or carbon-extended compounds. In this study, we describe a straightforward approach for synthesizing beta-boryl cyclopropane derivatives using an inexpensive copper catalyst with CO as the C1 source. This reaction, mediated by an in situ generated carbene intermediate, provided a wide range of cyclopropane-containing organoboron compounds in moderate to good yields.
