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Xiaofeng Wu - One of the best experts on this subject based on the ideXlab platform.
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The Chemistry of CO: Carbonylation
Chem, 2019Co-Authors: Jin-bao Peng, Hui-qing Geng, Xiaofeng WuAbstract:Summary Carbon monoxide is one of the most important C1 molecules in organic chemistry. Many novel procedures for its conversion have been developed, and some have even been industrialized. In this review, we discuss and categorize CO chemistry into four classes: (1) transition-metal-mediated Carbonylation, (2) strong-acid-initiated cationic Carbonylation, (3) anionic Carbonylation, and (4) free-radical Carbonylation. Relevant achievements are selected and discussed in detail.
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Copper-catalyzed carbonylative transformations of indoles with hexaketocyclohexane.
Chemical Communications, 2018Co-Authors: Zechao Wang, Xiaofeng WuAbstract:With hexaketocyclohexane octahydrate as the carbon monoxide source, a novel procedure for copper-catalyzed direct double Carbonylation of indoles has been established. Using alcohols as reaction partners, moderate to good yields of the desired double Carbonylation products have been obtained. Wide functional group tolerance and substrate scope can be observed.
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Recent Achievements in Carbonylation Reactions: A Personal Account
Synlett, 2016Co-Authors: Jin-bao Peng, Xinxin Qi, Xiaofeng WuAbstract:This account summarizes predominately our recent endeavors in developing CO gas-free Carbonylation reactions and the application of Carbonylation reactions in the synthesis of heterocycles. Mo(CO) 6 , aldehydes, DMF, formic acid and its esters were employed as greener CO sources, and a series of palladium-catalyzed gas-free Carbonylation reactions, including reductive Carbonylation, amino- and alkoxyCarbonylations, as well as carbonylative coupling reactions have been developed. Besides, we developed a series of Carbonylation-based domino reactions for the rapid construction of heterocyclic compounds. 1 Introduction 2 Green Carbonyl Sources 2.1 Mo(CO) 6 as the CO Source 2.2 DMF as the CO Source 2.3 Formic Acid and Formates as the CO Sources 3 Carbonylative Synthesis of Heterocycles 3.1 Insertion of One CO Molecule 3.1.1 Intramolecular Nucleophilic Cyclization of Acyl Palladium 3.1.2 Intermolecular Nucleophilic Cyclization of Acyl Palladium 3.1.3 Cyclization through Nucleophilic Substitution 3.2 Insertion of Two CO Molecules 4. Conclusion
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a convenient palladium catalyzed reductive Carbonylation of aryl iodides with dual role of formic acid
Chemistry: A European Journal, 2016Co-Authors: Xinxin Qi, Chongliang Li, Xiaofeng WuAbstract:Palladium-catalyzed reductive Carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive Carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive Carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source.
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aryl formate as bifunctional reagent applications in palladium catalyzed carbonylative coupling reactions using in situ generated co
Angewandte Chemie, 2014Co-Authors: Haoquan Li, Matthias Beller, Helfried Neumann, Xiaofeng WuAbstract:After decades of development, Carbonylation reac- tions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functional- group tolerance and could be applied in Carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields. Ever since the pioneering work of Heck and Schoenberg in 1974, palladium-catalyzed carbonylative transformations of aryl halides have undergone impressive developments. (1) It has now constituted one of the most efficient and widely used methodologies for constructing carbonyl-containing com- pounds, such as aldehydes, amides, esters, etc. (2) However, the high toxicity, and odorless and flammable character of CO gas means that transformations using CO gas must be operated with special care. Usually, autoclaves and well- ventilated fume hoods, equipped with special CO detectors and alarms, are required for these reactions, and has actually hindered the applications of such reactions. Given the disadvantages of using gaseous CO "CO-free"
Matthias Beller - One of the best experts on this subject based on the ideXlab platform.
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Carbonylations of Alkenes with CO Surrogates
Angewandte Chemie, 2014Co-Authors: Lipeng Wu, Ralf Jackstell, Matthias BellerAbstract:: Alkene Carbonylation reactions are important for the production of value-added bulk and fine chemicals. Nowadays, all industrial Carbonylation processes make use of highly toxic and flammable carbon monoxide. In fact, these properties impede the wider use of Carbonylation reactions in industry and academia. Hence, performing Carbonylations without the use of CO is highly desired and will contribute to the further advancement of sustainable chemistry. Although the use of carbon monoxide surrogates in alkene Carbonylation reactions has been reported intermittently in the last 30 years, only recently has this area attracted significant interest. This Minireview summarizes Carbonylation reactions of alkenes using different carbon monoxide surrogates.
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aryl formate as bifunctional reagent applications in palladium catalyzed carbonylative coupling reactions using in situ generated co
Angewandte Chemie, 2014Co-Authors: Haoquan Li, Matthias Beller, Helfried Neumann, Xiaofeng WuAbstract:After decades of development, Carbonylation reac- tions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functional- group tolerance and could be applied in Carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields. Ever since the pioneering work of Heck and Schoenberg in 1974, palladium-catalyzed carbonylative transformations of aryl halides have undergone impressive developments. (1) It has now constituted one of the most efficient and widely used methodologies for constructing carbonyl-containing com- pounds, such as aldehydes, amides, esters, etc. (2) However, the high toxicity, and odorless and flammable character of CO gas means that transformations using CO gas must be operated with special care. Usually, autoclaves and well- ventilated fume hoods, equipped with special CO detectors and alarms, are required for these reactions, and has actually hindered the applications of such reactions. Given the disadvantages of using gaseous CO "CO-free"
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transition metal catalyzed Carbonylation reactions of olefins and alkynes a personal account
Accounts of Chemical Research, 2014Co-Authors: Xiaofeng Wu, Lipeng Wu, Ralf Jackstell, Xianjie Fang, Helfried Neumann, Matthias BellerAbstract:Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO’s use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of Carbonylation catalysis, many important research questions and challenges remain.Notably, apart from academic developments, industry applies Carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are Carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via Carbonylation of methanol (Monsanto or Cativa process). The Carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions.In this Account, we discuss our work on various Carbonylations o...
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Ruthenium-catalysed alkoxyCarbonylation of alkenes with carbon dioxide
Nature Communications, 2014Co-Authors: Lipeng Wu, Ivana Fleischer, Ralf Jackstell, Matthias BellerAbstract:The conversion of alkenes to esters is performed on a large scale worldwide, but relies on the use of toxic and flammable carbon monoxide. Here, the authors show a catalytic system where carbon dioxide—normally unreactive, but cheap and abundant—can be employed instead. Alkene Carbonylations represent a major technology for the production of value-added bulk and fine chemicals. Nowadays, all industrial Carbonylation processes make use of highly toxic and flammable carbon monoxide. Here we show the application of abundantly available carbon dioxide as C1 building block for the alkoxyCarbonylations of industrially important olefins in the presence of a convenient and inexpensive ruthenium catalyst system. In our system, carbon dioxide works much better than the traditional combination of carbon monoxide and alcohols. The unprecedented in situ formation of carbon monoxide from carbon dioxide and alcohols permits an efficient synthesis of carboxylic acid esters, which can be used as detergents and polymer-building blocks. Notably, this transformation allows the catalytic formation of C–C bonds with carbon dioxide as C1 source and avoids the use of sensitive and/or expensive reducing agents (for example, Grignard reagents, diethylzinc or triethylaluminum).
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Oxidative Carbonylation Reactions
Transition Metal Catalyzed Carbonylation Reactions, 2013Co-Authors: Matthias Beller, Xiaofeng WuAbstract:In the last six chapters we discussed the transition metal catalyzed carbonylative activation of organohalogen (C–X, X = I, Br, Cl, OTf, etc.) compounds. They all have one common point in their reaction mechanism; taking a palladium catalyst, for example, the reactions start with Pd(0) and then go to Pd(II) after an oxidative addition. To summarize, the reactions all go through Pd(0) to Pd(II) and a Pd(0) cycle. But for oxidative Carbonylation reactions, the reactions go through Pd(II) to Pd(0) and a Pd(II) cycle. Clearly, oxidative Carbonylations need additional oxidants to reoxidize the Pd(0) to Pd(II), and various organic nucleophiles were applied as substrates in the presence of CO. One of the most obvious advantages for oxidative Carbonylation reactions is the oxidative addition step can be avoid which is more reluctant under CO atmosphere.
Yuhong Zhang - One of the best experts on this subject based on the ideXlab platform.
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pd ii catalyzed c sp2 h Carbonylation of biaryl 2 amine synthesis of phenanthridinones
Tetrahedron, 2013Co-Authors: Zunjun Liang, Jitan Zhang, Kai Wang, Yuhong ZhangAbstract:Abstract A Pd(OAc)2-catalyzed C(sp2)–H Carbonylation protocol of arenes under carbon monoxide atmosphere has been developed. The scope of the Carbonylation reaction is broad and tolerates a variety of useful functional groups. This reaction provides a novel and efficient method for the synthesis of biologically and pharmaceutically significant phenanthridinones.
Helfried Neumann - One of the best experts on this subject based on the ideXlab platform.
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aryl formate as bifunctional reagent applications in palladium catalyzed carbonylative coupling reactions using in situ generated co
Angewandte Chemie, 2014Co-Authors: Haoquan Li, Matthias Beller, Helfried Neumann, Xiaofeng WuAbstract:After decades of development, Carbonylation reac- tions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functional- group tolerance and could be applied in Carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields. Ever since the pioneering work of Heck and Schoenberg in 1974, palladium-catalyzed carbonylative transformations of aryl halides have undergone impressive developments. (1) It has now constituted one of the most efficient and widely used methodologies for constructing carbonyl-containing com- pounds, such as aldehydes, amides, esters, etc. (2) However, the high toxicity, and odorless and flammable character of CO gas means that transformations using CO gas must be operated with special care. Usually, autoclaves and well- ventilated fume hoods, equipped with special CO detectors and alarms, are required for these reactions, and has actually hindered the applications of such reactions. Given the disadvantages of using gaseous CO "CO-free"
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transition metal catalyzed Carbonylation reactions of olefins and alkynes a personal account
Accounts of Chemical Research, 2014Co-Authors: Xiaofeng Wu, Lipeng Wu, Ralf Jackstell, Xianjie Fang, Helfried Neumann, Matthias BellerAbstract:Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO’s use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of Carbonylation catalysis, many important research questions and challenges remain.Notably, apart from academic developments, industry applies Carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are Carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via Carbonylation of methanol (Monsanto or Cativa process). The Carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions.In this Account, we discuss our work on various Carbonylations o...
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palladium catalyzed oxidative Carbonylation reactions
Chemsuschem, 2013Co-Authors: Xiaofeng Wu, Helfried Neumann, Matthias BellerAbstract:: Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several Carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative Carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative Carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative Carbonylation reactions.
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Palladium‐Catalyzed Oxidative Carbonylation Reactions
Chemsuschem, 2013Co-Authors: Xiaofeng Wu, Helfried Neumann, Matthias BellerAbstract:: Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several Carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative Carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative Carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative Carbonylation reactions.
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ruthenium and rhodium catalyzed Carbonylation reactions
Chemcatchem, 2012Co-Authors: Xiaofeng Wu, Helfried NeumannAbstract:Over the last few decades, Carbonylation reactions have been accepted as important chemical transformations for both academic and industrial research. Carboxylic acid derivatives are the main product of Carbonylation and are widely used in organic synthesis and fine chemicals preparation. Carbonylation reactions can increase the carbon chain of parent molecules, while introducing a carbonyl group. Herein, the main developments on ruthenium- and rhodium-catalyzed Carbonylation are summarized. Compared with palladium catalysts, ruthenium and rhodium catalyzed reactions are a powerful method for activating CH bonds under mild and phosphine free conditions.
Zunjun Liang - One of the best experts on this subject based on the ideXlab platform.
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pd ii catalyzed c sp2 h Carbonylation of biaryl 2 amine synthesis of phenanthridinones
Tetrahedron, 2013Co-Authors: Zunjun Liang, Jitan Zhang, Kai Wang, Yuhong ZhangAbstract:Abstract A Pd(OAc)2-catalyzed C(sp2)–H Carbonylation protocol of arenes under carbon monoxide atmosphere has been developed. The scope of the Carbonylation reaction is broad and tolerates a variety of useful functional groups. This reaction provides a novel and efficient method for the synthesis of biologically and pharmaceutically significant phenanthridinones.