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Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
Author(s) -
Yang Ji,
Liu Jiawang,
Ge Yao,
Huang Weiheng,
Ferretti Francesco,
Neumann Helfried,
Jiao Haijun,
Franke Robert,
Jackstell Ralf,
Beller Matthias
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202015329
Subject(s) - chemistry , palladium , carbonylation , catalysis , isomerization , selectivity , organic chemistry , methanol , adipate , carbon monoxide , atom economy , homolysis , adipic acid , combinatorial chemistry , polymer chemistry , radical
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 (d t bpx) 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.