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, 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
Hongwei Shi, Jun Li, Tao Wang, Matthias Rudolph, A. Stephen K. Hashmi
Summary: A catalyst- and additive-free sunlight-induced strategy for the autoxidation of a wide range of aldehydes to carboxylic acids is described. This method utilizes air as the source of oxygen and sunlight as the light source, offering green, highly atom-efficient, and low-cost synthesis. The reaction can be easily scaled up and can proceed smoothly even at lower temperature and in natural light.
Article
Chemistry, Organic
Ming Chen, Yang Li, Zheng-Hui Guan
Summary: In this work, a palladium-catalyzed hydroalkoxycarbonylation and hydroxycarbonylation of cyclopent-3-en-1-ols is reported, which enables the synthesis of bridged bicyclic lactones and beta,gamma-unsaturated carboxylic acid. The reactivity of cyclopent-3-en-1-ols is controlled by the palladium catalyst and ligands. The reaction is additive-free and exhibits a broad substrate scope, allowing access to valuable synthetic and medical intermediates.
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
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
Yong-Mei Xiao, Yu Zhao, Jia-Qi Li, Jin-Wei Yuan, Liang-Ru Yang, Pu Mao, Wen-Peng Mai
Summary: A novel and convenient method for the synthesis of thioesters using palladium catalysis has been developed. This method allows for the coupling of various carboxylic acids with disulfides to produce thioesters in moderate to good yields. The accessibility of starting materials and the broad scope of substrates make this method a practical route for thioester synthesis without the use of toxic thiols or CO gas.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Leilei Wang, Yangyang Ma, Yuhang Jiang, Leiyang Lv, Zhiping Li
Summary: This study presents a manganese-catalyzed radical relay strategy for the remote trifluoromethylation-peroxidation of unactivated alkenes, delivering 1,6-difunctionalized products selectively under mild conditions. The electrophilic CF3 group is added to double bonds, generating remote C-centered radicals upon 1,5-HAT, which are efficiently trapped by Mn(n+)1OOBu-t species. t-BuOOH serves as both the oxidant and peroxy precursor in this transformation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Jianyu Dong, Xiuling Chen, Fangyan Ji, Lixin Liu, Lebin Su, Min Mo, Jian-Sheng Tang, Yongbo Zhou
Summary: In the presence of copper salt and molecular oxygen, a simple and direct aerobic oxidative esterification reaction of arylacetonitriles with alcohols/phenols is achieved, resulting in a broad range of aryl carboxylic acid esters in good to high yields. Copper salt plays multiple roles in the transformation, facilitating the oxygenation of C-H bond, cleavage of inert C-C bond, and formation of C-O bond in one pot without the need for any additional acids, bases, ligands, etc. This reaction provides a simple, direct, and efficient method for synthesizing functionalized esters, especially aryl benzoates, from readily available starting materials.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yuvraj A. Kolekar, Bhalchandra M. Bhanage
Summary: An efficient method for synthesizing tertiary amides from aryl boronic acids and inert tertiary amines via oxidative carbonylation was presented, with significantly reduced homocoupling biarylketone formation. The use of homogeneous PdCl2/CuI and heterogeneous Pd/C catalysts promotes C(sp(3))-N bond activation between tertiary amines and aryl boronic acids, utilizing a ligand-free, base-free, and recyclable catalyst system with molecular oxygen as an ideal oxidant.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Sonam, Vikki N. Shinde, Anil Kumar
Summary: A novel green method promoted by KPF6 has been developed for the synthesis of esters and amides, providing good to excellent yields (61-98%) under a wide range of reaction conditions. The method shows good performance with bioactive substrates and offers operational simplicity and sustainability, making it a practical and economically attractive approach for preparing esters and amides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ken Sakata, Yuuri Uehara, Shiona Kohara, Takeshi Yoshikawa, Yoshiaki Nishibayashi
Summary: In this study, the effects of propargylic substituents on the enantioselectivity and reactivity in propargylic substitution reactions were further investigated using density functional theory calculations. The results showed that substitution of a methyl group at the propargylic position could reverse the stereoselectivity, while substitution of a trifluoromethyl group for a methyl group was suggested to enhance the enantioselectivity.
Article
Chemistry, Multidisciplinary
Sean T. Goralski, Krystal M. Cid-Seara, Jenni J. Jarju, Laura Rodriguez-Lorenzo, Alec P. LaGrow, Michael J. Rose, Laura M. Salonen
Summary: The reactivity of a novel Re(i) catalyst is controlled by its interactions with a covalent organic framework (COF), allowing for different catalytic reactions depending on the local environment. The study highlights the potential of COFs in modulating the reactivity of homogeneous catalysts.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Han-Jun Ai, Yang Yuan, Xiao-Feng Wu
Summary: In this work, a pincer ruthenium-catalyzed heterocycle compatible alkoxycarbonylation of alkyl iodides has been developed, allowing efficient reaction with a variety of heterocyclic substrates.
Article
Chemistry, Multidisciplinary
Yusuke Morino, Takafumi Yatabe, Kosuke Suzuki, Kazuya Yamaguchi
Summary: The efficient aerobic oxidative esterification of ethylene glycol to various oxalic acid diesters has been achieved using CuCl/tetramethylethylenediamine/1,5-dimethyl-9-azanoradamantane N-oxyl catalyst. The reaction shows high selectivity for ethylene glycol-derived alcohols/hemiacetals even in the presence of other aliphatic primary alcohols, and the efficient esterification is enabled by the preferential bidentate coordination of ethylene glycol-derived alcohols/hemiacetals to the Cu(ii) species.
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
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
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, 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, 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
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, 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.
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
Fengxiang Zhu, Ziyan Li, Xiao-Feng Wu
Summary: A novel method for the nickel-catalyzed multicomponent aminofluoroalkylation/cyclization of styrenes with ethyl fluoroacetate and anilines has been developed, providing a general and efficient access to a diverse range of fluoro-gamma-lactams from simple and readily available starting materials. Control experiments confirmed the involvement of radical intermediates and ruled out the presence of 2-fluoro-N-phenylacetamide.