Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

The Pd­(cod)­Cl2-catalyzed alkoxycarbonylation of conjugated dienes to β,γ-unsaturated esters was approached by both intramolecular phosphinesulfonate L1 and intermolecular PPh3/PTSA in this study. However, the poor solubility of the Pd/L1 complex and the labile monodentate Pd/PPh3 structure restric...

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Published inJournal of organic chemistry Vol. 88; no. 2; pp. 882 - 892
Main Authors Zhang, Zi-Heng, Han, Li-Jun, Ma, Shuang-Shuang, Du, Yi-Ran, Yu, Zheng-Kun, Lin, Jin-Qing, Xu, Bao-Hua
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 20.01.2023
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Summary:The Pd­(cod)­Cl2-catalyzed alkoxycarbonylation of conjugated dienes to β,γ-unsaturated esters was approached by both intramolecular phosphinesulfonate L1 and intermolecular PPh3/PTSA in this study. However, the poor solubility of the Pd/L1 complex and the labile monodentate Pd/PPh3 structure restricts the system efficiency, especially for the scale-up application. By contrast, the stable and well-soluble bidentate Xantphos system allows for the quantitative formation of 3-pentenoate (96%) on a gram scale within 6 h in weakly alkaline N-methylpyrrolidone (NMP), which also functions as a basic site to promote the rate-limiting alcoholysis step while reducing the dosage of ligand to a theoretical value.
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content type line 23
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.2c02245