Article
Chemistry, Multidisciplinary
Fengqian Zhao, Han-Jun Ai, Xiao-Feng Wu
Summary: In this study, a novel copper-catalyzed method has been developed for the highly selective double carbonylation of alkyl bromides, yielding moderate to good yields of alpha-keto amides as the sole products. Under different conditions, controllable double- and mono-carbonylation can be achieved with alkyl iodides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Johanne Ling, Antoine Bruneau-Voisine, Guillaume Journot, Gwilherm Evano
Summary: In this study, a general copper-catalyzed carbonylative cross-coupling between amines and alkyl iodides was reported. The reaction showed good efficiency and broad substrate scope, making it potentially valuable for industrial applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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, 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, Organic
Fanni Bede, Laszlo Kollar, Nandor Lambert, Peter Huszthy, Peter Pongracz
Summary: Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were successfully performed under carbon monoxide atmosphere. The targeted amides were synthesized in moderate to good isolated yields without the need for acidic additives. The effect of chiral diphosphines on product distribution, including chemo-, regio-, and enantioselectivities, was also investigated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Lijun Lu, Feiyu Qiu, Hesham Alhumade, Heng Zhang, Aiwen Lei
Summary: This work demonstrated metal-controlled mono-and double-carbonylation reactions of alkanes with amines, resulting in the preparation of alkyl amides and alkyl alpha-ketoamides, with Co and Cu catalysis systems affording different selectivities.
Article
Chemistry, Multidisciplinary
Qiao Chu, Zhaoyue Feng, Sumin Zhang, Ping Liu, Peipei Sun
Summary: An electrochemical three-component reaction cascade Mumm rearrangement was developed for the synthesis of imides. Commercially available aryl acids, nitriles, and alkylbenzenes were used as substrates without pre-functionalization, and the reactions were conducted under transition metal- and chemical oxidant-free conditions. Subsequent hydrolysis or reduction of the imide products could be easily achieved to synthesize amides, as well as primary or tertiary amines.
Article
Chemistry, Multidisciplinary
Le-Cheng Wang, Bo Chen, Xiao-Feng Wu
Summary: A novel cobalt-catalyzed carbonylative coupling of ethers with amines has been achieved, leading to the synthesis of biologically active compounds. This protocol presents the first example of direct carbonylative reaction of ethers, providing an important method for the construction of alpha-carbonylated ethers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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, 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
Simone Grosso, Marcelina Mlynczak, Gwilherm Evano, Olivier Riant
Summary: An efficient and unprecedented cross-coupling reaction between acylzirconocenes and diaryliodonium tetrafluoroborates is reported. This method utilizes acylzirconocenes, readily prepared starting materials, and a low pressure of in situ generated carbon monoxide to synthesize a variety of alkyl-aryl-ketones under simple copper cyanide catalysis, without the need for additional ligands.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Qian Yu, Li Zhang, Yuhao He, Jinjing Pan, Hao Li, Guo-qing Bian, Xiaodan Chen, Gengwen Tan
Summary: The reaction of the carbazole ligand supported Ga(i) compound LGa(THF) (3) with 1-azido-4-(tert-butyl)benzene (ArN3) resulted in the first stable tetrazagallole LGaN4Ar2 (4) with a three-coordinate Ga atom. Reduction of 4 with elemental potassium led to the radical dimer {[K(18-c-6)](+)[4](-)}(2) featuring a strong antiferromagnetic interaction between the spin centers.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Changpeng Chen, Wenqing Guo, Deyong Qiao, Shaolin Zhu
Summary: We report a NiH-catalyzed asymmetric migratory hydroalkylation process for the efficient and selective construction of enantioenriched multi-substituted cycloalkanes. Through a dynamic kinetic asymmetric transformation (DYKAT), easily accessible racemic and isomeric mixtures of cycloalkenes could be directly utilized as starting materials, convergently producing highly regio-, diastereo-, and enantioselective chiral 1,2-cis disubstituted cycloalkanes. In addition, prochiral cyclic alkenes can also be employed, delivering chiral 1,2-cis disubstituted cycloalkanes through desymmetrization process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Tanakorn Wonglakhon, Dirk Zahn
Summary: In this study, a tailor-made force field was developed to capture the interactions between gallium ions and species in ammonia solution, which bridged the characterization of GaN precipitation and the modeling of GaN crystals. Quantum mechanical characterization of Ga coordination clusters was used for parameterization and refinement of the force field, leading to good agreement in both structural features and formation energy. The potential applications of the models in larger scale molecular dynamics simulations were demonstrated by analyzing the arrangement of amide and imide defects during GaN crystal growth.
Article
Chemistry, Organic
Guangming Wei, Yue Sun, Dongling Zheng, Shiqi Qiu, Zhengkai Chen, Xiao-Feng Wu
Summary: A heating-induced desulfurization annulation of CF3-imidoyl sulfoxonium ylides and isothiocyanates has been developed for the synthesis of 2-trifluoromethylquinolines. The reaction proceeds under metal- and additive-free conditions, providing various biologically valuable derivatives with high efficiency.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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, Multidisciplinary
Peng Huang, Guang'an Zhang, Zechao Wang, Junliang Wu
Summary: In this study, a silver catalyzed alkoxylation of benzylic C(sp(3))-H bonds using potassium persulfate as an oxidant at room temperature was reported. This strategy exhibited good functional-group tolerance, site selectivity, and chemoselectivity, allowing the synthesis of corresponding benzyl ethers in the presence of various primary, secondary, and tertiary alcohol nucleophiles. Mechanistic insights into the possible radical pathways were obtained through experimental studies, and a possible mechanism for this method was proposed.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Chang-Sheng Kuai, Bing-Hong Teng, Yingying Zhao, Xiao-Feng Wu
Summary: A method for the selective deoxygenative and alkoxy carbonylation of alcohols using boronic acids via palladium catalysis has been developed. The choice of activators determines the different selectivities. Carbodiimide activator promotes the formation of ketones through deoxygenative carbonylation, while azo activator leads to ester formation via alkoxy carbonylation. This study expands the substrate scope and allows for the use of base-sensitive boronic acid substrates. It contributes to the understanding and control of chemoselectivity in carbonylation chemistry.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Fengxiang Zhu, Jiajia Luo, Xiao-Feng Wu
Summary: In this study, a novel copper-catalyzed direct carbodiazenylation method was developed for the synthesis of alkylarylazo compounds. The reaction is carried out under redox neutral conditions, allowing the use of highly functionalized substrates and producing a wide range of diazenes in moderate to good yields. Importantly, this process enables the straightforward preparation of indoles under mild conditions.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Chang-Sheng Kuai, Bing-Hong Teng, Rui Lai, Yingying Zhao, Guohui Li, Xiao-Feng Wu
Summary: A new method has been developed for the dicarbonylation of amines using the catalytic ending PdII-H in a buffer condition, allowing two incompatible catalytic systems to work simultaneously. This protocol shows excellent regioselectivity and broad substrate scope. Combined experimental and computational studies reveal that the reaction proceeds through a Pd0/PdII-H relay-catalytic cycle.
JOURNAL OF CATALYSIS
(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
Shangyuan Wang, Jiajun Zhao, Jun Ying, Xiao-Feng Wu
Summary: This study developed a palladium-catalyzed one-pot two-step radical mediated carbonylative cyclization method to construct polycyclic 3,4-dihydroquinolin-2-(1H)-one scaffolds using perfluoroalkyl iodides and Mo-(CO)(6) with 1,7-enynes. Various polycyclic 3,4-dihydroquinolin-2-(1H)-one derivatives containing perfluoroalkyl and carbonyl units were synthesized with high yields. Moreover, modification of several bioactive molecules was demonstrated using this protocol.
Article
Chemistry, Organic
Guangming Wei, Dongling Zheng, Chen Li, Zhengkai Chen, Xiao-Feng Wu
Summary: Trifluoromethyl-substituted 1,2-dihydroquinoxalines and diimines can be synthesized efficiently through a base-mediated cascade reaction involving the unusual N-N bond cleavage and rearrangement of azo compounds.
Article
Chemistry, Organic
Le-Cheng Wang, Nai-Xian Sun, Chang-Sheng Wang, Kai Guo, Xiao-Feng Wu
Summary: The direct concurrent installation of amide and ester groups across olefin motifs is a powerful and promising functionalization tool in organic chemistry. Here, a ligand-free cobalt-catalyzed four-component radical relay carbonylative difunctionalization of ethylene for the synthesis of 4-oxobutanoates has been developed, providing a highly atom-economical approach for the production of valuable C4 building blocks.
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.
Review
Chemistry, Multidisciplinary
Zuguang Yang, Guangming Wei, Zhengkai Chen, Xiao-Feng Wu
Summary: Recent research has focused on the direct synthesis of trifluoromethyl-containing heterocycles from TFAICs and its derivatives, such as TFAIHs and TFISYs. Cascade annulation reactions of these synthons with suitable coupling partners have proven to be a powerful tool for constructing a variety of trifluoromethyl-substituted heterocycles. TFAICs and derivatives are advantageous due to their easy availability and handling, relative stability and safety, and high reactivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Xing-Wei Gu, Xiao-Feng Wu
Summary: Transition metal-catalyzed carbonylation of alkyl halides is an efficient method for synthesizing aliphatic carbonyl-containing compounds. This paper discusses recent developments in the carbonylation reactions of alkyl bromides and chlorides catalyzed by abundant metals.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Le-Cheng Wang, Xiao-Feng Wu
Summary: In this study, we have developed an unprecedented and general method for the direct synthesis of various alpha-amino acid derivatives by activating inert C-H bonds. By introducing an appropriate electron-withdrawing group, we successfully modulated the nucleophilicity and polarity of the reaction, resulting in a broad substrate scope and excellent tolerance of sensitive functional groups in this catalytic strategy.
JOURNAL OF CATALYSIS
(2023)
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)
