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Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters

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 pa...

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Autores principales: Yang, Ji, Liu, Jiawang, Ge, Yao, Huang, Weiheng, Ferretti, Francesco, Neumann, Helfried, Jiao, Haijun, Franke, Robert, Jackstell, Ralf, Beller, Matthias
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8251817/
https://www.ncbi.nlm.nih.gov/pubmed/33448531
http://dx.doi.org/10.1002/anie.202015329
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author Yang, Ji
Liu, Jiawang
Ge, Yao
Huang, Weiheng
Ferretti, Francesco
Neumann, Helfried
Jiao, Haijun
Franke, Robert
Jackstell, Ralf
Beller, Matthias
author_facet Yang, Ji
Liu, Jiawang
Ge, Yao
Huang, Weiheng
Ferretti, Francesco
Neumann, Helfried
Jiao, Haijun
Franke, Robert
Jackstell, Ralf
Beller, Matthias
author_sort Yang, Ji
collection PubMed
description 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.
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spelling pubmed-82518172021-07-07 Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters Yang, Ji Liu, Jiawang Ge, Yao Huang, Weiheng Ferretti, Francesco Neumann, Helfried Jiao, Haijun Franke, Robert Jackstell, Ralf Beller, Matthias Angew Chem Int Ed Engl Research Articles 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. John Wiley and Sons Inc. 2021-03-03 2021-04-19 /pmc/articles/PMC8251817/ /pubmed/33448531 http://dx.doi.org/10.1002/anie.202015329 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Research Articles
Yang, Ji
Liu, Jiawang
Ge, Yao
Huang, Weiheng
Ferretti, Francesco
Neumann, Helfried
Jiao, Haijun
Franke, Robert
Jackstell, Ralf
Beller, Matthias
Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
title Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
title_full Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
title_fullStr Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
title_full_unstemmed Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
title_short Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
title_sort efficient palladium‐catalyzed carbonylation of 1,3‐dienes: selective synthesis of adipates and other aliphatic diesters
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8251817/
https://www.ncbi.nlm.nih.gov/pubmed/33448531
http://dx.doi.org/10.1002/anie.202015329
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