Article
Chemistry, Physical
Pierre-Louis Lagueux-Tremblay, Celestin Augereau, Pranav Nair, Kwan Ming Tam, Bruce A. Arndtsen
Summary: The use of metal catalysis to form potent acylating agents is an important approach to expand the application of carbonylation reactions. However, the reductive elimination of these reactive products has been a challenge, making these reactions often high temperature, high pressure, and limited in scope. In this study, a mild and versatile palladium catalyzed carbonylative method was developed to generate electrophilic acyl-DMAP salts by exploiting the counterion. The weakly coordinating triflate anion was found to destabilize Pd(II) and enable irreversible reductive elimination, while ligand design facilitated the rapid activation of aryl or vinyl triflates. This approach allows palladium catalyzed carbonylations to be carried out under exceptionally mild conditions, with low catalyst loading and using readily available C(sp2)-triflate reagents.
Article
Chemistry, Physical
Pierre-Louis Lagueux-Tremblay, Celestin Augereau, Pranav Nair, Kwan Ming Tam, Bruce A. Arndtsen
Summary: The use of metal catalysis to form potent acylating agents is an important method to broaden the applicability of carbonylation reactions. However, the reductive elimination of these reactive products has presented a challenge, making the reactions often high temperature and high pressure, and limited in scope. In this study, a mild and versatile palladium catalyzed carbonylative method was developed to generate electrophilic acyl-DMAP salts. The use of triflate anion as a counterion destabilizes Pd(II) and allows for irreversible reductive elimination, while ligand design enables the rapid activation of aryl or vinyl triflates.
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
Peng Wang, Ji Yang, Kangkang Sun, Helfried Neumann, Matthias Beller
Summary: The direct palladium-catalyzed selective carbonylative coupling of less reactive aryl chlorides with primary and secondary amines is achieved using a palladium/Xantphos catalyst system and cesium chloride as an additive. This reaction shows high conversion for various aryl chlorides and good functional group compatibility.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Bowen Hu, Haoqiang Zhao, Yu Wu, Patrick J. Walsh
Summary: A novel, selective and high-yielding palladium-catalyzed carbonylative arylation of weakly acidic benzylic and heterobenzylic C(sp(3))-H bonds with aryl bromides has been achieved. The system allows access to diverse alpha-aryl or alpha,alpha-diaryl ketones, which are commonly found in biologically active compounds. The use of Josiphos SL-J001-1-based palladium catalyst enables the carbonylative arylation without the formation of direct coupling byproducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Dan Li, Li Wei, Chaorong Qi, Wenfang Xiong, Hongjian Liu, Huanfeng Jiang
Summary: A palladium-catalyzed direct carbonylation of aryl bromides with carbon dioxide as the carbonyl source has been developed, providing an efficient route to a variety of aryl carboxylic acids in moderate to high yields. The method has many advantages including the use of a simple palladium catalyst system, wide substrate scope, good functional group tolerance, high yields, and easy scalability.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Tanuja Tewari, Rohit Kumar, Samir H. Chikkali
Summary: This study reports the use of an iron catalyst in carbonylation reactions to convert alkynes to alpha,beta-unsaturated esters. The reaction is operationally simple and allows the synthesis of various unsaturated esters.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Tanuja Tewari, Rohit Kumar, Samir H. Chikkali
Summary: An iron catalyst is reported for the hydroalkoxycarbonylation of alkynes in the presence of CO, affording α,β-unsaturated esters. The reaction is operationally simple and tolerates various functional groups, offering facile access to a range of compounds.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Organic
Chen Su, Wen-Hua Xu, Rui-Li Guo, Xing-Long Zhang, Xue-Qing Zhu, Ya-Ru Gao, Yong-Qiang Wang
Summary: This study developed a novel method for the synthesis of aporphine analogues, utilizing an intramolecular dehydrogenative coupling of two inert aryl C-H bonds. The method not only exhibits high compatibility with various functional groups, but has also been further applied for the synthesis of natural products aporphine and zenkerine.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jin-He Na, Xiang Liu, Jia-Wen Jing, Jing Wang, Xue-Qiang Chu, Mengtao Ma, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A step-economical and efficient one-pot reaction was developed for the direct cross-coupling of aryl fluorosulfate with aryl bromide. This reaction, conducted at room temperature in THF solvent, does not require the use of preprepared/commercial organometallic reagents. By utilizing nickel catalyst, magnesium turnings, and lithium chloride, the desired biaryls were obtained in moderate to good yields with reasonable functional group compatibility.
Article
Chemistry, Multidisciplinary
Fu-Peng Wu, Yang Yuan, Jiawang Liu, Xiao-Feng Wu
Summary: An unprecedented and challenging defluorinative carbonylation reaction was achieved with the first example of defluorinative carbonylative coupling established using a Pd/Cu cooperative catalyst system. This methodology, using gem-difluoroalkenes and aryl iodides as substrates, provides flexible and facile access to privileged alpha-fluorochalcones under mild reaction conditions in moderate-to-excellent yields. Mechanistic studies demonstrated that transmetalation between palladium and copper intermediates is a crucial step in the catalytic cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Multidisciplinary
Tiefeng Xu, Qi Wang, Zeyi Yang, Lili Yi, Jian-Shu Wang, Wangyang Lu, Jun Ying, Xiao-Feng Wu
Summary: The palladium supported on graphitic carbon nitride (Pd/g-C3N4) catalyzed carbonylative reaction of aryl bromides and arylboronic acids successfully constructed various diaryl ketones using TFBen as the CO source, resulting in moderate to good yields.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Xueling Liu, Tongshun An, Zhiping Yin, Wenzhou Zhang
Summary: A new palladium-catalyzed reductive double carbonylation of nitroarenes with aryl halides has been developed for the synthesis of benzoxazin-4-ones. This method utilizes Mo(CO)(6) as a reductant and solid carbonyl sources, and can produce benzoxazin-4-one derivatives in moderate to good yields. Importantly, it avoids the use of toxic CO gas and is applicable for late-stage modification of estrone.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Tian-Hong Jing, Kai-Chun Zhao, Guang-Hui Shi, Yi-Ying Zhuang, Xiao-Chao Chen, Xiao-Li Zhao, Yong Lu, Ye Liu
Summary: A series of bis-P,O-hybrid ligands were synthesized and characterized. The crystal structures showed that the ligand of L2 acted as a typical trans-positioned diphosphine as observed in the complexes Pd(L2)(OAc)2 and Pd(L2)Cl2, but also potentially as a P,P,O-tripodal pincer. Under mild conditions, L2 enabled Pd(OAc)2 to exhibit remarkable performance in the alkoxycarbonylation of vinyl arenes with high activity and excellent regioselectivity.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Zhiping Yin, Weidong Shi, Xiao-Feng Wu
Summary: This review presents the advances in transition-metal-catalyzed carbonylative multifunctionalization of alkynes, which is of great significance for the construction of multisubstituted carbonyl-containing derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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, Physical
Fengqian Zhao, Jian-Xing Xu, Fu-Peng Wu, Xiao-Feng Wu
Summary: This communication describes a copper-catalyzed selectivity-reversed borocarbonylation. In the presence of CuOAc/BuPAd2 catalytic system, a series of unactivated terminal alkenes were transformed into β-boryl ketones in moderate yields, using sterically hindered alkyl bromides as the electrophiles.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Guangming Wei, Jiajun Zhang, Haoyuan Wang, Zhengkai Chen, Xiao-Feng Wu
Summary: A novel method was developed for the construction of diversely functionalized azaspiro[4,5]-tetraenones and quinolines through the incorporation of CF3 and Se groups into heterocycles. The method exhibited good regioselectivity and its synthetic utility was demonstrated by scale-up reaction and further modification of the obtained products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Chang-Sheng Kuai, Bing-Hong Teng, Da-Lie An, Yingying Zhao, Xiao-Feng Wu
Summary: A palladium-catalyzed carbonylation of 2-trifluoromethyl-1,3-enynes has been developed, providing access to multisubstituted conjugated dienes. This method exhibits excellent regio- and exclusive (E)-stereoselectivity and demonstrates broad substrate scope with both amines and alcohols as reaction partners, showing promising functional group tolerance.
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, Physical
Yuanrui Wang, Xiao-Feng Wu
Summary: A palladium-catalyzed redox-neutral dicarbonylation of terminal alkynes has been developed, using hydroxylamine as both a nucleophile and a potential oxidant. Maleimides were synthesized in moderate yields under relatively mild conditions without the addition of equivalent oxidants. This reaction involves Pd-H addition to the alkyne and the role of hydroxylamine ester intermediate as an internal oxidant via nucleophilic attack.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Da-Lie An, Le-Cheng Wang, Youcan Zhang, Xiao-Feng Wu
Summary: A new method for synthesizing esters via cobalt-catalyzed carbonylative acetylation of phenols has been developed. In this approach, DTBP serves as the methyl source and reacts with various phenols under low CO pressure (5 bar), resulting in moderate to good yields of the desired esters.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Ping Wei, Yiwen Zhu, Jun Ying, Xiao-Feng Wu
Summary: Cobalt(II) salt has been widely used as a non-noble metal catalyst for direct C-H bond functionalization. In this study, we developed a cobalt-catalyzed reaction for the rapid construction of 2-alkoxylindole scaffolds from the C-H cleavage and alkoxylation of indoles with alcohols. The reaction proceeded well with Co(acac)2 as the catalyst, yielding a variety of 2-alkoxylindole derivatives in moderate to high yields. Control experiments suggested a radical process involving Co(III) species as the active catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Organic
Xiao-Feng Wu, Paul J. Dyson, Bruce A. Arndtsen
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Youcan Zhang, Zhi-Peng Bao, Chang-Sheng Kuai, Xiao-Feng Wu
Summary: Here, we have developed a direct and effective synthesis strategy for sulfur-containing carboxylic acid derivatives through copper/visible light catalyzed ring-opening carbonylation of sulfonium salts. The protocol utilizes photoredox to selectively cleave the C(sp3)-S bond of sulfonium salts, while sequentially functionalizing to form vicinal C-C and C-X (X = O or N) bonds in the presence of carbon monoxide and nucleophiles. Various substrates were successfully transformed into desired carbonylated products with moderate to good yields, displaying good functional group tolerance and excellent chemoselectivity. Importantly, this approach can be easily extended to late-stage modification of bioactive molecules.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Yiwen Zhu, Jing Wang, Jun Ying, Xiao-Feng Wu
Summary: A cobalt-catalyzed C-H activation and isocyanide insertion reaction of tryptamine derivatives has been developed, leading to the synthesis of indole-2-carboxamide scaffolds. The reaction showed good efficiency in producing a variety of indole-2-carboxamides in moderate to high yields, using Co(OAc)2.4H2O as the non-noble catalyst. Mechanistic experiments revealed the involvement of a Co(III) species as the active catalyst in a non-radical reaction pathway. Notably, the silver salt oxidant could be recycled and reused.
Article
Chemistry, Organic
Yan-Hua Zhao, Xing-Wei Gu, Xiao-Feng Wu
Summary: This paper reports a ligand-free visible-light-induced manganese-catalyzed carbonylation reaction for the synthesis of various amides. The method offers advantages such as low cost and low toxicity, and can proceed effectively at ambient temperature and pressure.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Fengxiang Zhu, Jianxin Xue, Xiao-Feng Wu
Summary: An Fe(II)-catalyzed three-component 1,2-difunctionalization of alkenes with di-tert-butyl peroxide as the methylation reagent has been reported. This method enables 1,2-methylamination and 1,2-methylarylation of various alkenes using nucleophiles such as aromatic amines, pyrrole, and indoles. The simplicity of this protocol allows for the rapid synthesis of complex molecules from simple starting materials.
Article
Chemistry, Physical
Xing Ge, Xiuyu Fang, Ren-Guan Miao, Xinxin Qi, Xiao-Feng Wu
Summary: A general and efficient protocol has been developed for the synthesis of acetamide-functionalized benzofurans using a palladium-catalyzed intramolecular cyclization and reductive aminocarbonylation reaction. The reaction proceeds in a single step, resulting in structure-defined benzofurans with acetamides as attractive functional groups. Various acetamide-functionalized benzofurans were obtained with moderate to good yields and good functional group compatibility using Mo(CO)6 as both CO source and reductant.
JOURNAL OF CATALYSIS
(2023)
