{"title":"末端烯烃非均相氢甲酰化反应的支链区域选择性:“两步法”及动力学优化","authors":"Muhan Li, Yifan Sun, Weixiang Wang, Zhangxinyu Fan, Xiao Chen, Shule Zhang, Huanjun Wang, Hongwei Niu, Tiefeng Wang, Boyang Liu, Qin Zhong","doi":"10.1021/acscatal.5c04539","DOIUrl":null,"url":null,"abstract":"Hydroformylation of olefins to aldehydes is an important reaction in the chemical industry. The development of heterogeneous catalysts has attracted much attention due to their ease of separation and environmental friendliness. Although researchers have focused more on linear products, branched aldehydes also have wide applications, serving as important chemical products or intermediates in fragrance, pharmaceutical, and other fields. In this work, we propose a tandem “two-step process” method to obtain high regioselectivity of branched aldehydes with the same catalyst, even when using terminal olefins as the reactants. The method includes the isomerization process of the terminal olefins to internal olefins and the subsequent heterogeneous hydroformylation process, converting internal olefins to branched aldehydes. The kinetic model of heterogeneous hydroformylation of internal olefins is also established, and the predicted <i>b</i>/<i>l</i> ratio under different reaction conditions is consistent with the experimental results. After the optimization of reaction conditions, the highest <i>b</i>/<i>l</i> ratio of the ″two-step process” for 1-octene reaches 33.34, which is 39 times higher than that obtained by direct hydroformylation and surpasses all branched regioselectivities reported in other literature, to the best of our knowledge. This work not only deepens the mechanistic understanding of heterogeneous hydroformylation of both terminal and internal olefins but also provides inspiration and practical guidance for the industrial production of branched aldehydes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Branched Regioselectivity in the Heterogeneous Hydroformylation of Terminal Olefins: A “Two-Step Process” Method and Kinetic Optimization\",\"authors\":\"Muhan Li, Yifan Sun, Weixiang Wang, Zhangxinyu Fan, Xiao Chen, Shule Zhang, Huanjun Wang, Hongwei Niu, Tiefeng Wang, Boyang Liu, Qin Zhong\",\"doi\":\"10.1021/acscatal.5c04539\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Hydroformylation of olefins to aldehydes is an important reaction in the chemical industry. The development of heterogeneous catalysts has attracted much attention due to their ease of separation and environmental friendliness. Although researchers have focused more on linear products, branched aldehydes also have wide applications, serving as important chemical products or intermediates in fragrance, pharmaceutical, and other fields. In this work, we propose a tandem “two-step process” method to obtain high regioselectivity of branched aldehydes with the same catalyst, even when using terminal olefins as the reactants. The method includes the isomerization process of the terminal olefins to internal olefins and the subsequent heterogeneous hydroformylation process, converting internal olefins to branched aldehydes. The kinetic model of heterogeneous hydroformylation of internal olefins is also established, and the predicted <i>b</i>/<i>l</i> ratio under different reaction conditions is consistent with the experimental results. After the optimization of reaction conditions, the highest <i>b</i>/<i>l</i> ratio of the ″two-step process” for 1-octene reaches 33.34, which is 39 times higher than that obtained by direct hydroformylation and surpasses all branched regioselectivities reported in other literature, to the best of our knowledge. This work not only deepens the mechanistic understanding of heterogeneous hydroformylation of both terminal and internal olefins but also provides inspiration and practical guidance for the industrial production of branched aldehydes.\",\"PeriodicalId\":9,\"journal\":{\"name\":\"ACS Catalysis \",\"volume\":\"4 1\",\"pages\":\"\"},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2025-10-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Catalysis \",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acscatal.5c04539\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c04539","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Branched Regioselectivity in the Heterogeneous Hydroformylation of Terminal Olefins: A “Two-Step Process” Method and Kinetic Optimization
Hydroformylation of olefins to aldehydes is an important reaction in the chemical industry. The development of heterogeneous catalysts has attracted much attention due to their ease of separation and environmental friendliness. Although researchers have focused more on linear products, branched aldehydes also have wide applications, serving as important chemical products or intermediates in fragrance, pharmaceutical, and other fields. In this work, we propose a tandem “two-step process” method to obtain high regioselectivity of branched aldehydes with the same catalyst, even when using terminal olefins as the reactants. The method includes the isomerization process of the terminal olefins to internal olefins and the subsequent heterogeneous hydroformylation process, converting internal olefins to branched aldehydes. The kinetic model of heterogeneous hydroformylation of internal olefins is also established, and the predicted b/l ratio under different reaction conditions is consistent with the experimental results. After the optimization of reaction conditions, the highest b/l ratio of the ″two-step process” for 1-octene reaches 33.34, which is 39 times higher than that obtained by direct hydroformylation and surpasses all branched regioselectivities reported in other literature, to the best of our knowledge. This work not only deepens the mechanistic understanding of heterogeneous hydroformylation of both terminal and internal olefins but also provides inspiration and practical guidance for the industrial production of branched aldehydes.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.