The Experts below are selected from a list of 360 Experts worldwide ranked by ideXlab platform
Matthias Beller - One of the best experts on this subject based on the ideXlab platform.
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pd catalyzed selective carbonylation of gem difluoroalkenes a practical synthesis of difluoromethylated esters
Angewandte Chemie, 2019Co-Authors: Ji Yang, Francesco Ferretti, Ralf Jackstell, Matthias BellerAbstract:: The first catalyst for the Alkoxycarbonylation of gem-difluoroalkenes is described. This novel catalytic transformation proceeds in the presence of Pd(acac)2 /1,2-bis((di-tert-butylphosphan-yl)methyl)benzene (btbpx) (L4) and allows for an efficient and straightforward access to a range of difluoromethylated esters in high yields and regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology as the key step.
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selective palladium catalysed synthesis of diesters Alkoxycarbonylation of a co2 butadiene derived δ lactone
Green Chemistry, 2017Co-Authors: Francesco Ferretti, Ralf Jackstell, M. Sharif, S. Dastgir, F. Ragaini, Matthias BellerAbstract:Novel unsaturated C10 diesters are produced via the Alkoxycarbonylation of δ-lactone 1 (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one), derived from the telomerization of CO2 and butadiene. The key for the selective valorization of 1 is the use of a catalytic system based on PdCl2, a chelating phosphine bearing electron-withdrawing groups and an acidic promoter. The unsaturated C10 methyl diester can be easily hydrogenated on Pd/C under mild conditions to afford its corresponding saturated diester. Subsequent hydrogenation using the homogeneous [Ru(acac)3]/Triphos catalysts gives 2-ethyloctane-1,8-diol in high yield. The overall procedure allows synthesizing new building blocks for the manufacturing of renewable polymers and polymer processing materials.
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efficient palladium catalyzed Alkoxycarbonylation of bulk industrial olefins using ferrocenyl phosphine ligands
Angewandte Chemie, 2017Co-Authors: Kaiwu Dong, Ralf Jackstell, Xianjie Fang, Rui Sang, Robert Franke, Anke Spannenberg, Helfried Neumann, Matthias BellerAbstract:The development of ligands plays a key role and provides important innovations in homogeneous catalysis. In this context, we report a novel class of ferrocenyl phosphines for the Alkoxycarbonylation of industrially important alkenes. A basic feature of our ligands is the combination of sterically hindered and amphoteric moieties on the P atoms, which leads to improved activity and productivity for Alkoxycarbonylation reactions compared to the current industrial state-of-the-art ligand 1,2-bis((di-tert-butylphosphino)methyl)benzene). Advantageously, palladium catalysts with these novel ligands also enable such transformations without additional acid under milder reaction conditions. The practicability of the optimized ligand was demonstrated by preparation on >10 g scale and its use in palladium-catalyzed carbonylations on kilogram scale.
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highly active and efficient catalysts for Alkoxycarbonylation of alkenes
Nature Communications, 2017Co-Authors: Kaiwu Dong, Ralf Jackstell, Xianjie Fang, Robert Franke, Anke Spannenberg, Helfried Neumann, Samet Gulak, Matthias BellerAbstract:Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general Alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.
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the scope and mechanism of palladium catalysed markovnikov Alkoxycarbonylation of alkenes
Nature Chemistry, 2016Co-Authors: Kaiwu Dong, Ralf Jackstell, Helfried Neumann, Haijun Jiao, Matthias BellerAbstract:The selective formation of Markovnikov products in carbonylation reactions is a challenging problem, especially from unactivated substrates. Now, a highly Markovnikov-selective Alkoxycarbonylation reaction is described using a catalyst system based on palladium and the cataCXium ligand POMeCy(Ph). The resulting branched carboxylates are important structural components in many flavour and fragrance products.
Bingfeng Shi - One of the best experts on this subject based on the ideXlab platform.
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stereoselective Alkoxycarbonylation of unactivated c sp 3 h bonds with alkyl chloroformates via pd ii pd iv catalysis
Nature Communications, 2016Co-Authors: Gang Liao, Xuesong Yin, Kai Chen, Qi Zhang, Shuoqing Zhang, Bingfeng ShiAbstract:Several examples on Pd-catalysed carbonylation of methyl C(sp^3)–H bonds with gaseous CO via Pd(II)/Pd(0) catalysis have been reported. However, methylene C(sp^3)–H carbonylation remains a great challenge, largely due to the lack of reactivity of C–H bonds and the difficulty in CO migratory insertion. Herein, we report the stereoselective Alkoxycarbonylation of both methyl and methylene C(sp^3)–H bonds with alkyl chloroformates through a Pd(II)/Pd(IV) catalytic cycle. A broad range of aliphatic carboxamides and alkyl chloroformates are compatible with this protocol. In addition, this process is scalable and the directing group could be easily removed under mild conditions with complete retention of configuration.
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pd ii catalyzed oxidative Alkoxycarbonylation of 2 phenoxypyridine derivatives with co and alcohols
Organic and Biomolecular Chemistry, 2014Co-Authors: Bin Liu, Bingfeng Shi, Huaizhi JiangAbstract:A Pd(II)-catalyzed oxidative Alkoxycarbonylation of phenol derivatives with atmospheric pressure of CO–O2 and alcohols has been achieved. The reaction provides an efficient strategy for the synthesis of carboxylic esters and can be applied to the late-stage modification of complex molecules.
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efficient synthesis of carboxylic esters via palladium ii catalyzed direct Alkoxycarbonylation of arenes with co and alcohols
Synlett, 2013Co-Authors: Bin Liu, Bingfeng ShiAbstract:An efficient palladium(II)-catalyzed procedure for the Alkoxycarbonylation of arenes and heteroarenes with atmospheric pressure carbon monoxide and alcohols was developed to synthesize aryl carboxylic esters.
Ralf Jackstell - One of the best experts on this subject based on the ideXlab platform.
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pd catalyzed selective carbonylation of gem difluoroalkenes a practical synthesis of difluoromethylated esters
Angewandte Chemie, 2019Co-Authors: Ji Yang, Francesco Ferretti, Ralf Jackstell, Matthias BellerAbstract:: The first catalyst for the Alkoxycarbonylation of gem-difluoroalkenes is described. This novel catalytic transformation proceeds in the presence of Pd(acac)2 /1,2-bis((di-tert-butylphosphan-yl)methyl)benzene (btbpx) (L4) and allows for an efficient and straightforward access to a range of difluoromethylated esters in high yields and regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology as the key step.
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selective palladium catalysed synthesis of diesters Alkoxycarbonylation of a co2 butadiene derived δ lactone
Green Chemistry, 2017Co-Authors: Francesco Ferretti, Ralf Jackstell, M. Sharif, S. Dastgir, F. Ragaini, Matthias BellerAbstract:Novel unsaturated C10 diesters are produced via the Alkoxycarbonylation of δ-lactone 1 (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one), derived from the telomerization of CO2 and butadiene. The key for the selective valorization of 1 is the use of a catalytic system based on PdCl2, a chelating phosphine bearing electron-withdrawing groups and an acidic promoter. The unsaturated C10 methyl diester can be easily hydrogenated on Pd/C under mild conditions to afford its corresponding saturated diester. Subsequent hydrogenation using the homogeneous [Ru(acac)3]/Triphos catalysts gives 2-ethyloctane-1,8-diol in high yield. The overall procedure allows synthesizing new building blocks for the manufacturing of renewable polymers and polymer processing materials.
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efficient palladium catalyzed Alkoxycarbonylation of bulk industrial olefins using ferrocenyl phosphine ligands
Angewandte Chemie, 2017Co-Authors: Kaiwu Dong, Ralf Jackstell, Xianjie Fang, Rui Sang, Robert Franke, Anke Spannenberg, Helfried Neumann, Matthias BellerAbstract:The development of ligands plays a key role and provides important innovations in homogeneous catalysis. In this context, we report a novel class of ferrocenyl phosphines for the Alkoxycarbonylation of industrially important alkenes. A basic feature of our ligands is the combination of sterically hindered and amphoteric moieties on the P atoms, which leads to improved activity and productivity for Alkoxycarbonylation reactions compared to the current industrial state-of-the-art ligand 1,2-bis((di-tert-butylphosphino)methyl)benzene). Advantageously, palladium catalysts with these novel ligands also enable such transformations without additional acid under milder reaction conditions. The practicability of the optimized ligand was demonstrated by preparation on >10 g scale and its use in palladium-catalyzed carbonylations on kilogram scale.
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highly active and efficient catalysts for Alkoxycarbonylation of alkenes
Nature Communications, 2017Co-Authors: Kaiwu Dong, Ralf Jackstell, Xianjie Fang, Robert Franke, Anke Spannenberg, Helfried Neumann, Samet Gulak, Matthias BellerAbstract:Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general Alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.
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Selective palladium-catalysed synthesis of diesters: Alkoxycarbonylation of a CO2-butadiene derived delta-lactone
'Royal Society of Chemistry (RSC)', 2017Co-Authors: F. Ferretti, Ralf Jackstell, M. Sharif, S. Dastgir, F. Ragaini, M. BellerAbstract:Novel unsaturated C-10 diesters are produced via the Alkoxycarbonylation of delta-lactone 1 (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one), derived from the telomerization of CO2 and butadiene. The key for the selective valorization of 1 is the use of a catalytic system based on PdCl2, a chelating phosphine bearing electron-withdrawing groups and an acidic promoter. The unsaturated C-10 methyl diester can be easily hydrogenated on Pd/C under mild conditions to afford its corresponding saturated diester. Subsequent hydrogenation using the homogeneous [Ru(acac)(3)]/Triphos catalysts gives 2-ethyloctane-1,8-diol in high yield. The overall procedure allows synthesizing new building blocks for the manufacturing of renewable polymers and polymer processing materials
Wenjing Xiao - One of the best experts on this subject based on the ideXlab platform.
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cobalt ii catalyzed Alkoxycarbonylation of aliphatic amines via c n bond activation
Organic Letters, 2019Co-Authors: Xuan Jiang, Wenjing XiaoAbstract:The first cobalt-catalyzed deaminative Alkoxycarbonylation reaction was described for the conversion of readily available primary alkyl amines to synthetically versatile esters with moderate to high yields. This transformation shows good functional group compatibility and can serve as a powerful tool for the modification of alkyl amine-containing complex natural products and drug molecules.
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metal free room temperature radical Alkoxycarbonylation of aryldiazonium salts through visible light photoredox catalysis
ChemInform, 2015Co-Authors: Wei Guo, Yue Wang, Yani Wang, Jiarong Chen, Wenjing XiaoAbstract:This is the first visible-light-induced (blue LED) radical alkoxycarboxylation of aryldiazonium salts using carbon monoxide gas.
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metal free room temperature radical Alkoxycarbonylation of aryldiazonium salts through visible light photoredox catalysis
Angewandte Chemie, 2015Co-Authors: Wei Guo, Yue Wang, Yani Wang, Jiarong Chen, Wenjing XiaoAbstract:The first radical alkoxycarboxylation of aryldiazonium salts using CO gas through visible-light-induced photoredox catalysis (16 W blue LEDs) has been developed. This reaction is entirely metal-free, is carried out at room temperature with a low loading of an organic dye as a photocatalyst (0.5 mol %), and provides a wide range of arylcarboxylic acid esters in high yields. Importantly, this photocatalytic system can be successfully extended to other carboxylation reactions.
Robert Franke - One of the best experts on this subject based on the ideXlab platform.
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phosphite catalyzed Alkoxycarbonylation of aryl diazonium salts
Organic and Biomolecular Chemistry, 2018Co-Authors: Robert FrankeAbstract:In this communication, an interesting phosphite-catalyzed Alkoxycarbonylation of aryl diazonium salts has been reported. At room temperature and under CO pressure, moderate to good yields of the desired esters can be produced in the absence of bases or any other additives.
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efficient palladium catalyzed Alkoxycarbonylation of bulk industrial olefins using ferrocenyl phosphine ligands
Angewandte Chemie, 2017Co-Authors: Kaiwu Dong, Ralf Jackstell, Xianjie Fang, Rui Sang, Robert Franke, Anke Spannenberg, Helfried Neumann, Matthias BellerAbstract:The development of ligands plays a key role and provides important innovations in homogeneous catalysis. In this context, we report a novel class of ferrocenyl phosphines for the Alkoxycarbonylation of industrially important alkenes. A basic feature of our ligands is the combination of sterically hindered and amphoteric moieties on the P atoms, which leads to improved activity and productivity for Alkoxycarbonylation reactions compared to the current industrial state-of-the-art ligand 1,2-bis((di-tert-butylphosphino)methyl)benzene). Advantageously, palladium catalysts with these novel ligands also enable such transformations without additional acid under milder reaction conditions. The practicability of the optimized ligand was demonstrated by preparation on >10 g scale and its use in palladium-catalyzed carbonylations on kilogram scale.
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highly active and efficient catalysts for Alkoxycarbonylation of alkenes
Nature Communications, 2017Co-Authors: Kaiwu Dong, Ralf Jackstell, Xianjie Fang, Robert Franke, Anke Spannenberg, Helfried Neumann, Samet Gulak, Matthias BellerAbstract:Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general Alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.
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ligand controlled palladium catalyzed Alkoxycarbonylation of allenes regioselective synthesis of α β and β γ unsaturated esters
ChemInform, 2015Co-Authors: Jie Liu, Robert Franke, Ralf Jackstell, Qiang Liu, Matthias BellerAbstract:The palladium-catalyzed regioselective Alkoxycarbonylation of allenes with aliphatic alcohols allows to produce synthetically useful α,β- and β,γ-unsaturated esters in good yields. Efficient selectivity control is achieved in the presence of appropriate ligands. Using Xantphos as the ligand, β,γ-unsaturated esters are produced selectively in good yields. In contrast, the corresponding α,β-unsaturated esters are obtained with high regioselectivity in the presence of PPh2Py as the ligand. Preliminary mechanistic studies revealed that these two catalytic processes proceed by different reaction pathways. In addition, this novel protocol was successfully applied to convert an industrially available bulk chemical, 1,2-butadiene, into dimethyl adipate, which is a valuable feedstock for polymer and plasticizer syntheses, with high yield and TON (turnover number).
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a unique palladium catalyst for efficient and selective Alkoxycarbonylation of olefins with formates
Chemsuschem, 2013Co-Authors: Ivana Fleischer, Ralf Jackstell, Robert Franke, Reiko Jennerjahn, Daniela Cozzula, Matthias BellerAbstract:Forget about CO! Carbonylations are among the most important homogeneously catalyzed reactions in the chemical industry, but typically require carbon monoxide. Instead, straightforward and efficient Alkoxycarbonylations of olefins can proceed with alkyl formates in the presence of a specific palladium catalyst. Aromatic, terminal aliphatic, and internal olefins are carbonylated to give industrially important linear esters at low catalyst loadings.