REGIOSELECTIVE HYDROALKOXYCARBONYLATION OF 1.3-BUTADIENE, 1.5-HEXADIENE, AND 1.7-OCTADIENE USING PALLADIUM-PHOSPHINE CATALYTIC SYSTEMS

Abzal Meirembekuly Azimbay; Nurbolat Zharylkasynuly Kudaibergenov; Kairzhan Mustafinovich Shalmagambetov; Alua Erzhanovna Alikeyeva; Zarrina Bakytzhan; Meruert Khalykkyzy Zykai

doi:10.51580/2025-4.2710-1185.57

Authors

Abzal Meirembekuly Azimbay Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University
Nurbolat Zharylkasynuly Kudaibergenov Department of Chemistry, Kazakh National Women's Teacher Training University
Kairzhan Mustafinovich Shalmagambetov Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University
Alua Erzhanovna Alikeyeva Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University
Zarrina Bakytzhan Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University
Meruert Khalykkyzy Zykai Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University

DOI:

https://doi.org/10.51580/2025-4.2710-1185.57

Keywords:

alkadienes, hydroalkoxycarbonylation, palladium catalysts, ethyl esters, regioselectivity

Abstract

Hydroalkoxycarbonylation of dienes offers a straightforward and atom-economic route to valuable esters derived from simple unsaturated feedstocks and carbon monoxide. In this work, we investigated the regioselective hydroalkoxycarbonylation of three representative substrates: 1.3-butadiene, 1.5-hexadiene, and 1.7-octadiene, using palladium-phosphine catalysts in ethanol at 120°C under 2.5 MPa CO. Two catalysts, [PdCl₂(PPh₃)₂] and [Pd(PPh₃)₄], were tested in combination with additional PPh₃ and p-toluenesulfonic acid. Across all three dienes, the reactions consistently favored formation of the linear ester, with yields increasing as the diene chain length grew and conjugation decreased: from 2.31% for ethyl 4-pentenoate (from 1,3-butadiene) up to 32.08% for ethyl 8-nonenoate (from 1,7-octadiene). The superior performance of Pd(PPh₃)₄ compared with PdCl₂(PPh₃)₂highlights the importance of electron-rich Pd(0) species in stabilizing acyl intermediates and sustaining catalytic turnover. These findings not only clarify how catalyst structure and substrate features influence reactivity in diene hydroalkoxycarbonylation but also provide practical guidance for tailoring conditions to enhance linear selectivity. Such insights expand the synthetic potential of this methodology for producing C₅-C₁₀ esters relevant to polymer, plasticizer, fragrance, and fine-chemical applications.

Author Biographies

Abzal Meirembekuly Azimbay, Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University

Master of Engineering Sciences

Nurbolat Zharylkasynuly Kudaibergenov , Department of Chemistry, Kazakh National Women's Teacher Training University

Associate Professor

Kairzhan Mustafinovich Shalmagambetov , Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University

Doctor of Chemical Sciences

Alua Erzhanovna Alikeyeva , Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University

PhD student

Zarrina Bakytzhan , Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University

PhD student

Meruert Khalykkyzy Zykai , Center of Physicochemical Methods of Research and Analysis at Al-Farabi Kazakh National University

Senior Researcher