Rh-catalyzed hydroformylation of allyl acetate toward 4-acetoxybutyraldehyde: The crucial step in production of 1,4-butanediol via hydroformylation/hydrogenation sequence

•Hydroformylation of allyl acetate as determining step for production of 1,4-butanediol (1,4-BDO) via hydroformylation-hydrogenation sequence.•Hydroformylation of the functional olefin of allyl acetate with Xantphos-modified Rh(acac)(CO)2 catalyst.•The target product of 4-hydroxylbutanal obtained in...

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Published in:Molecular catalysis 2023-07, Vol.545, p.113209, Article 113209
Main Authors: Shi, Guang-Hui, Chen, Xiao-Chao, Jing, Tian-hong, Zhuang, Yi-Ying, Lu, Yong, Liu, Ye
Format: Article
Language:English
Subjects:
1,4-butanediol
Allyl acetate
Diphosphine
Hydroformylation
Rhodium catalyst
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Summary:•Hydroformylation of allyl acetate as determining step for production of 1,4-butanediol (1,4-BDO) via hydroformylation-hydrogenation sequence.•Hydroformylation of the functional olefin of allyl acetate with Xantphos-modified Rh(acac)(CO)2 catalyst.•The target product of 4-hydroxylbutanal obtained in 80% yield alongside trace presence of its branched isomer.•Xantphos-Rh(acac)(CO)2 catalytic system recyclable for 10 runs without obvious activity loss. The synthesis protocol for 1,4-butanediol via two-step hydroformylation-hydrogenation sequence using allyl acetate as the starting material has attracted much attention in industry. In this work, the first-step hydroformylation of allyl acetate determining the overall efficiency of this protocol was studied. Based on the phosphine screening and reaction condition optimization allyl acetate, Xantphos-modified Rh(acac)(CO)2 catalytic system proved highly efficient for hydroformylation of allyl acetate, giving the target product of 4-acetoxybutanal in the yield of 80%. This catalytic system is advantageous with excellent regioselectivity to the linear product of 4-acetoxybutanal as well as the recyclability up to 10 runs without activity loss, demonstrating its remarkable stability required for large-scale application. The control experiments were conducted to shed light on the involved reaction pathways for generation of target 4-acetoxybutanal and the related side-products. [Display omitted]
ISSN:2468-8231
2468-8231
DOI:10.1016/j.mcat.2023.113209