JOURNAL OF CATALYSIS
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2024
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IF 6.5
Xiao-Chao Chen,Wen-Di Guo,Guo-Sheng Zhang,Long-Gen Hu,Yong Lu,Ye Liu
Pd-catalyzed hydroxycarbonylation of alkynes with CO and H 2 O is a promising alternative for one-step synthesis of α,β-unsaturated carboxylic acids advantageous with 100 % atom-economy, but suffering from rapid catalyst deactivation and unavoidable side reactions like polymerization and hydration while the auxiliary acid-additive is required as a co-catalyst. Herein, free of any auxiliary acid-additive and under mild conditions (0.5 MPa, 60 °C, 3 h), a flexible zwitterionic phosphine of L1 containing a mono-phosphino-fragment and a hydrophilic sulfonate group (–SO 3 - ) conferred to Pd(OAc) 2 catalyst efficient performance for hydroxycarbonylation of terminal alkynes, affording the branched α,β-unsaturated carboxylic acids in the yields of 85 ∼ 91 % with 100 % regioselectivity. In addition, the developed L1 -Pd(OAc) 2 system was so stable that it could be recycled for 30 runs with well-maintained activity and selectivity, which proved the most active and stable to date under acid-additive-free condition.
研究领域:
有机化学
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催化化学
✓ 已验证
DOI
高影响因子
ChemistryOpen
·
2022
·Vol. 11
·期 4
·e202100301
·
IF 2.63
Yin-Qing Yao,Kai-Chun Zhao,Yi-Ying Zhuang,Xiao-Chao Chen,Yong Lu,Ye Liu
Graphical The one-pot synthesis of 2,5-furandicarboxylic acid from 2-furoic acid was achieved for the first time using a Pd-catalyzed bromination-hydroxycarbonylation tandem reaction in HOAc-NaOAc buffer. The synthesis process provides major improvements compared to previously reported methods, namely using biomass-based 2-furoic acid as low-cost raw material, one-pot synthesis without isolation of intermediate product, and no need for an acidification procedure. The one-pot synthesis of 2,5-furandicarboxylic acid from 2-furoic acid with a yield of 57 % was achieved for the first time using a Pd-catalyzed bromination-hydroxycarbonylation tandem reaction in HOAc-NaOAc buffer. This synthetic protocol shows major improvements compared to previously reported methods, such as using biomass-based 2-furoic acid as low-cost raw material, one-pot synthesis without isolation of intermediate products, and no need for an acidification procedure. Experiments indicate that the involved Xantphos-modified Pd-catalyst and the buffer solution play significant promoting roles for each individual reaction whereas Br 2 (as the brominating reagent) had a negative effect on the second hydroxycarbonylation step, while CO was deleterious for the first bromination step. Hence, in this practical one-pot synthesis, Br 2 should be consumed in the first bromination step as fully as possible, and CO is introduced after the first bromination step has been completed.
研究领域:
有机化学
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生物质化学
✓ 已验证
DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 19
·5336-5344
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IF 9.405
Da Yang,Huan Liu,Lei Liu,Wen-Di Guo,Yong Lu,Ye Liu
An amphiphilic tri-functional ligand (L1) containing a Lewis acidic phosphonium cation, a phosphino-fragment and a hydrophilic sulfonate anion (–SO3−) enabled Pd(OAc)2 to efficiently co-catalyze the hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids. These incorporated functional groups synergistically promoted the reaction, which proved more effective than the ligands lacking –SO3− and/or phosphonium and the mechanical mixtures of the individual functional groups independently. The molecular structure of Pd-L1 indicated that –SO3− in L1 served as a secondary O-donor ligand with reversible coordinating ability, cooperating with the phosphino-fragment to stabilize the Pd-catalyst. The in situ FT-IR analysis verified that the formation and stability of Pd–H active species in charge of hydroxycarbonylation were dramatically facilitated by the presence of L1. It was believed that, over the L1-based Pd-catalyst, H2O was cooperatively activated by the Lewis acidic phosphonium via “acid–base pair” interaction (H2O → P(V)+) and by the hydrophilic SO3−via hydrogen bonding (SO3−⋯H2O), giving rise to the formation of dimeric and mono-nuclear Pd–H species driven by reversible SO3−-coordination. In addition, the L1-based Pd-catalyst could be immobilized in the ionic liquid [Bmim]NTf2 for six-run recycling uses without obvious activity loss and detectable metal leaching.
研究领域:
有机化学
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催化化学
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材料科学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Long-Gen Hu,Guo-Sheng Zhang,Guang-Hui Shi,Jian-Guo Qian,Hai-Jing Wang,Ye Liu
The Pd-catalyzed aminocarbonylation as well as hydroxycarbonylation of terminal alkynes was achieved with aid of a sulfonate-built-in zwitterionic phosphine ( L2 ), under acid-additive free condition. With L2 -Pd(OAc) 2 catalytic system, the terminal alkynes smoothly converted to the corresponding α,β -unsaturated carbonyl compounds (amides or carboxylic acids) in moderate to excellent isolated yields, with 100 % branched regio-selectivity. It was believed that L2 with the matched steric-demand and the bulit-in-SO 3 - -unit not only tuned the catalytic performance of Pd(OAc) 2 to activate CO and alkyne but also exhibited the synergetic activating ability towards the nucleophiles of (primary/secondary) amines or H 2 O via developing hydrogen-bond interaction, which facilitated the observed successful carbonylation. It means the developed L2 -Pd(OAc) 2 system could serve as a bifunctional catalyst.
研究领域:
有机化学
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催化化学
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配位化学
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合成化学
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物理有机化学
✓ 已验证
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高影响因子
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