Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

Zi Heng Zhang; Li Jun Han; Shuang Shuang Ma; Yi Ran Du; Zheng Kun Yu; Jin Qing Lin; Bao Hua Xu

doi:10.1021/acs.joc.2c02245

Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

Zi Heng Zhang, Li Jun Han, Shuang Shuang Ma, Yi Ran Du, Zheng Kun Yu, Jin Qing Lin^*, Bao Hua Xu^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	882-892
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	88
Issue number	2
DOIs	https://doi.org/10.1021/acs.joc.2c02245
Publication status	Published - 20 Jan 2023

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title = "Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes",

abstract = "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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doi = "10.1021/acs.joc.2c02245",

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T1 - Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

AU - Zhang, Zi Heng

AU - Han, Li Jun

AU - Ma, Shuang Shuang

AU - Du, Yi Ran

AU - Yu, Zheng Kun

AU - Lin, Jin Qing

AU - Xu, Bao Hua

PY - 2023/1/20

Y1 - 2023/1/20

N2 - 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.

AB - 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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Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

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