- Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes
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The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.
- Yang, Ji,Liu, Jiawang,Neumann, Helfried,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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- Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
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The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.
- Yang, Ji,Liu, Jiawang,Ge, Yao,Huang, Weiheng,Ferretti, Francesco,Neumann, Helfried,Jiao, Haijun,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 9527 - 9533
(2021/03/08)
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- SYNTHESIS OF ALIPHATIC POLYCARBOXYLIC ACID
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The present invention provides a method for synthesizing an aliphatic polycarboxylic acid, the method comprising the steps of: (a) dehydrating a polyhydroxycarboxlic acid using a rhenium-based catalyst to produce an unsaturated polycarboxylic acid precursor; and (b) performing a hydrogenation reaction on the unsaturated polycarboxylic acid precursor to produce the aliphatic polycarboxylic acid.
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Page/Page column 10
(2016/03/22)
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- CHEMICAL PROCESS TO CONVERT MUCIC ACID TO ADIPIC ACID
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The present invention provides a method of synthesizing an ester of a saturated carboxylic acid from a saturated polyhydroxycarboxylic acid by performing a deoxydehydration reaction and a hydrogen transfer reaction.
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Page/Page column 17
(2015/06/18)
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- Highly efficient chemical process to convert mucic acid into adipic acid and DFT studies of the mechanism of the rhenium-catalyzed deoxydehydration
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The production of bulk chemicals and fuels from renewable bio-based feedstocks is of significant importance for the sustainability of human society. Adipic acid, as one of the most-demanded drop-in chemicals from a bioresource, is used primarily for the large-volume production of nylon-6,6 polyamide. It is highly desirable to develop sustainable and environmentally friendly processes for the production of adipic acid from renewable feedstocks. However, currently there is no suitable bio-adipic acid synthesis process. Demonstrated herein is the highly efficient synthetic protocol for the conversion of mucic acid into adipic acid through the oxorhenium-complex-catalyzed deoxydehydration (DODH) reaction and subsequent Pt/C-catalyzed transfer hydrogenation. Quantitative yields (99 %) were achieved for the conversion of mucic acid into muconic acid and adipic acid either in separate sequences or in a one-step process. Taking a dip: A highly efficient synthetic protocol has been developed for the conversion of mucic acid into adipic acid by the oxorhenium-complex-catalyzed deoxydehydration reaction and subsequent Pt/C-catalyzed transfer hydrogenation. Quantitative yields were achieved for the conversion of mucic acid into muconic acid and adipic acid esters either through separate sequences or through a one-pot process.
- Li, Xiukai,Wu, Di,Lu, Ting,Yi, Guangshun,Su, Haibin,Zhang, Yugen
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supporting information
p. 4200 - 4204
(2014/05/06)
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