Article
Chemistry, Multidisciplinary
Mariana P. Darbem, Henrique A. Esteves, Robert A. Burrow, Antonio A. Soares-Paulino, Daniel C. Pimenta, Helio A. Stefani
Summary: A novel Mo-catalyzed carbonylative Sonogashira cross-coupling between 2-iodoglycals and terminal alkynes is reported herein. The reaction shows significant improvements compared to a previously published Pd-catalyzed procedure by allowing the use of unprotected sugar derivatives as starting materials and tolerating substrates with chelating groups. The utility of the glyco-alkynone products as a platform for further functionalization is also demonstrated by synthesizing glycoflavones via Au-catalyzed 6-endo-dig cyclization.
Review
Chemistry, Multidisciplinary
Shaifali, Sheetal, Pralay Das
Summary: The carbonylative reactions using supported palladium catalysts under CO conditions are popular for synthesizing various compounds. Despite the poisoning effect of CO on palladium, advancements have been made to achieve high yields in recent years.
Review
Chemistry, Multidisciplinary
Li-Jie Cheng, Neal P. Mankad
Summary: Transition metal-catalyzed carbonylation reactions are an effective method to introduce oxygen functionality into organic compounds. However, challenges such as the use of noble metals as catalysts and the reactivity of certain substrates remain.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Dmitrii Kalinin, Trond Ulven
Summary: A chemoselective Pd-mediated carbonylative Negishi-type catalytic protocol for the synthesis of (hetero)-aryl ketones is described. The protocol utilizes the PEPPSI-IPr precatalyst and CO gas at atmospheric pressure to facilitate the carbonylative coupling between various C-(sp3)-hybridized organozinc reagents and a wide range of aryl iodides, including substrates with aldehyde, aniline, phenol, or carboxylic acid groups, and heteroaryls.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sebastien A. Roy, Jose Zgheib, Cuihan Zhou, Bruce A. Arndtsen
Summary: This study presents a palladium-catalyzed, multicomponent synthesis of indolizines. By forming a high-energy mesoionic pyridine-based 1,3-dipole, which can spontaneously undergo cycloaddition with alkynes, this method provides a way to prepare indolizines from combinations of commercially available or easily generated reagents, such as 2-bromopyridines, imines and alkynes.
Article
Chemistry, Organic
Baptiste Picard, Takahide Fukuyama, Ilhyong Ryu
Summary: An improved carbonylation method for amide bond formation between aryl iodides and aromatic amines is presented, which does not require a phosphine ligand unlike conventional Pd catalysis. The catalyst system consists of bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). This method allows the synthesis of various aromatic amides and can be scaled to gram order synthesis under low carbon monoxide pressure.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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, Organic
Qingqiang Tian, Shasha Xu, Chiying Zhang, Xinyi Liu, Xiangwei Wu, Yahui Li
Summary: An interesting palladium-catalyzed procedure for the direct carbonylative thiomethylation of aromatic amine derivatives with 4-methylthio-2-butanone is developed. Using 4-methylthio-2-butanone as (methylthio) transfer agent, a variety of corresponding thioesters are obtained with moderate to good yields under base-free condition. In addition, good functional group tolerance can be observed.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Pratik R. Chheda, Nicholas Simmons, David P. Schuman, Zhicai Shi
Summary: In this study, a DNA-compatible carbonylative Suzuki coupling reaction was reported for the synthesis of di(hetero)aryl ketones, which are important structural motifs. The developed method is mild, suitable for large-scale production, and provides a source of new chemical matter for DNA-encoded library screens.
Article
Chemistry, Multidisciplinary
Diedie Wang, Wanglv Lang, Wan Wang, Qizhuang Zou, Chunliang Yang, Fei Liu, Tianxiang Zhao
Summary: Copper hydride (CuH) complexes have been proposed as key intermediates in synthesis and catalysis. In this study, a highly efficient strategy for CuH-catalyzed N-methylation of aromatic and aliphatic amines was developed using paraformaldehyde and polymethylhydrosiloxane (PMHS) under mild reaction conditions. The reaction proceeded smoothly without additives to produce the corresponding N-methylated products using cyclic(alkyl)(amino)carbene (CAAC)CuH as a reaction intermediate, which resulted from a reaction between PMHS and (CAAC)CuCl.
Review
Chemistry, Physical
Jian-Xing Xu, Chang-Sheng Kuai, Bo Chen, Xiao-Feng Wu
Summary: This review focuses on the research progress of transition-metal-catalyzed carbonylation reactions, with an emphasis on the carbonylation of aliphatic carbon nucleophiles and the application of different reagents.
Article
Chemistry, Physical
Sangeth Jenthra, Totan Mondal, Gregor Kemper, Marcus Lantzius-Beninga, Markus Hoelscher, Walter Leitner
Summary: A highly chemo- and regioselective decarboxylative Heck-type coupling of carboxylic acids and terminal olefins was achieved using a catalytic system composed of Pd(OAc)(2) in the presence of phosphine-sulfonamido ligands. The bulky ligand L1 favored the formation of 1,1-disubstituted branched olefins with high selectivity, while the less bulky ligand L2 resulted in the formation of 1,2-disubstituted linear products in high yield. Detailed mechanistic investigation revealed that the aryl substituent at the sulfonamide group of ligand L1 favored 1,2-insertion, while the less bulky ligand L2 favored 2,1-insertion.
Article
Chemistry, Organic
Lingyun Yao, Yan Shang, Jian-Shu Wang, Ailin Pan, Jun Ying, Xiao-Feng Wu
Summary: This palladium-catalyzed carbonylative synthesis efficiently converts 2-alkynylanilines and aryl iodides into N-acyl indoles using TFBen as the CO source, resulting in high yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Masoumeh Jadidi Nejad, Akbar Heydari
Summary: In this study, a heterogeneous palladium catalyst system supported on MRGO@CoAl-LDH was synthesized for reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions. The catalyst was characterized using various techniques and showed good reusability for multiple cycles with high product yield. Formic acid was successfully applied as a safe and efficient alternative to CO and H2 gases in the reactions.
APPLIED ORGANOMETALLIC 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
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, 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.
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, 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)
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)
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)
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)
