JOURNAL OF CATALYSIS
·
2020
·
IF 7.888
Lei Liu,Xiao-Chao Chen,Shu-Qing Yang,Yin-Qing Yao,Yong Lu,Ye Liu
Formic acid (FA) is one kind of important bulk chemicals, which is recognized as a sustainable and eco-friendly energy carrier to transport H 2 via dehydrogenation or CO via decarbonylation. Expectantly, FA upon decomposition into H 2 and CO could be used as the syngas alternative for hydroformylation. In this paper, the behaviors of FA to release H 2 as well as CO following the distinct pathways were carefully investigated for the first time, and then established a new hydroformylation protocol free of syngas. It was found that the atmospheric hydroformylation of olefins with formic acid (FA) as syngas alternative was smoothly fulfilled over Xantphos ( L1 ) modified Rh-catalyst under mild conditions (80 °C, Rh concentration 1 mol %, 14 h), resulting in >90% conversion of the olefins along with the high selectivity to the target aldehydes (>93%). By using FA as syngas source, the side-reaction of olefin-hydrogenation was greatly depressed. The in situ FT-IR and the high-pressure 1 H NMR spectroscopic analyses were applied to reveal how FA behaves dually as CO surrogate and hydrogen source over L1 -Rh(acac)(CO) 2 catalytic system, based on which the deeply insight into the catalytic mechanism of hydroformylation of olefins with FA as syngas alternative was offered.
研究领域:
催化化学
·
绿色化学
·
能源化学
✓ 已验证
DOI
高影响因子
ChemCatChem
·
2019
·Vol. 12
·期 5
·1376-1384
·
IF 4.495
Wen-Di Guo,Lei Liu,Shu-Qing Yang,Xiao-Chao Chen,Yong Lu,Giang VO-Thanh,Ye Liu
Graphical Synergetic catalysis : The one-pot tandem bis-alkoxycarbonylation of alkynes was accomplished over the bi-functional catalytic system containing Xantphos-modified Pd-complex and Lewis super-acid of Al(OTf) 3 . Via the synergetic catalysis, the involved Xantphos-modified Pd-complex was responsible for the activation of CO and the alkynes through coordination to Pd-center while Al(OTf) 3 was in charge of the activation of the alcohol to facilitate the formation of [Pd−H] + active species. Tandem bis-alkoxycarbonylation of alkynes allows for the preparation of 2-substituted succinates from alkynes and nucleophile alcohol via two successive alkoxycarbonylation with advantages of 100 % atomic economy and simplified one-pot operation. Herein, the one-pot tandem bis-alkoxycarbonylation of alkynes was accomplished over the bi-functional catalytic system containing Xantphos-modified Pd-complex and Lewis super-acid of Al(OTf) 3 . It was found that, via the synergetic catalysis, the involved Xantphos-modified Pd-complex was responsible for the activation of CO and the alkynes through coordination to Pd-center while Al(OTf) 3 was in charge of the activation of the alcohol to facilitate the formation of [Pd−H] + active species. The in situ high-pressure FT-IR analysis, coupled with 1 H/ 13 C NMR spectral characterizations, confirmed that the introduced Al(OTf) 3 with intensive oxophilicity (via acid-base pair interaction) was able to activate nucleophilic MeOH to be a reliable proton-donor ( i. e . hydride-source) to warrant the formation and stability of [Pd−H] + species upon the oxidation of Pd 0 by H + (Pd 0 +H + →[Pd II −H] + ). Over the developed bi-functional catalytic system, the yields of the target diesters were obtained in the range of 36∼86 % in this sequence with the wide substrate scope.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2026
·
IF 6.5
Yuyong Zhang,Yuanjun Zhao,Yuanyuan Zhu,Yudi Wu,Zhaozhan Wang,Jinglin Mu,Yong Yang
The integration of superior homogeneous catalytic activity with the practical advantages of facile separation and robust recyclability of heterogeneous systems remains a grand challenge. Here, we report a heterogenized bidentate phosphine ligand, constructed by integrating commercial Xantphos into a hypercrosslinked porous polymer, as a versatile platform for Pd-catalyzed alkoxycarbonylation. The tailored polymer, featuring a high surface area, hierarchical pores, and chemical robustness, provides privileged coordination microenvironments. It empowers highly efficient alkoxycarbonylation of diverse alkenes with various alcohols, including monoalcohols, diols, and polyols, to produce valuable esters with activity and selectivity comparable to its homogeneous molecular counterpart. Moreover, the catalytic system enables the in-situ formation of a robust Pd catalyst, wherein Pd nanoparticles are stabilized and uniformly dispersed via strong Pd-P coordination. This resulting catalyst demonstrates exceptional durability, being readily recycled over ten times without significant degradation in performance. This work pioneers a versatile platform for ligand immobilization that effectively bridges homogeneous efficiency with heterogeneous durability, unlocking efficient and sustainable pathways for carbonylation and other ligand-mediate transformations.
✓ 已验证
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2023
·
IF 3.6
Zi-Heng Zhang,Li-Jun Han,Shuang-Shuang Ma,Yi-Ran Du,Zheng-Kun Yu,Jin-Qing Lin,Bao-Hua Xu
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.
研究领域:
有机化学
·
催化
·
合成化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）