Synthesis of Atropisomeric MeOBIPHEP Analogues and Their Application in Silver-Catalyzed Cycloisomerization of Allenols

Synthesis ◽  
2016 ◽  
Vol 48 (19) ◽  
pp. 3309-3316 ◽  
Author(s):  
Florent Le Boucher d’Herouville ◽  
Anthony Millet ◽  
Michelangelo Scalone ◽  
Véronique Michelet
Keyword(s):  
Catalytic System ◽  
Diphosphine Ligands ◽  
Reaction Conditions ◽  
Palladium Catalyzed ◽  
Alcohol Moiety

The preparation of novel MeOBIPHEP atropisomeric chiral congener ligands via an efficient palladium-catalyzed P–C coupling key step is described. We demonstrate that these palladium-catalyzed conditions are compatible with the brominated MeOBIPHEP backbone. The reaction conditions for asymmetric silver-catalyzed cycloisomerization of γ-allenols were optimized, leading to the first enantioselective catalytic system employing atropisomeric diphosphine ligands as the chiral inducer. The process follows a major 5-exo cyclization via addition of the alcohol moiety to the π-activated allenyl intermediate, leading to vinyltetrahydrofurans with enantiomeric ratios up to 91.5:8.5.

Palladium-Catalyzed Anti-Markovnikov Oxidation of Aromatic and Aliphatic Alkenes to Terminal Acetals and Aldehydes

Synthesis ◽  
2020 ◽  
Author(s):  
Yasuyuki Ura
Keyword(s):  
Organic Compounds ◽  
Catalytic System ◽  
Recent Progress ◽  
Short Review ◽  
Nucleophilic Attack ◽  
Reaction Conditions ◽  
Terminal Alkenes ◽  
Palladium Catalyzed ◽  
Substrate Addition ◽  
Cyclic Alkenes

AbstractCatalytic anti-Markovnikov (AM) oxidation of terminal alkenes can provide terminally oxyfunctionalized organic compounds. This short review mainly summarizes our recent progress on the Pd-catalyzed AM oxidations of aromatic and aliphatic terminal alkenes to give terminal acetals (oxidative acetalization) and aldehydes (Wacker-type oxidation), along with related reports. These reactions demonstrate the efficacy of the PdCl2(MeCN)2/CuCl/electron-deficient cyclic alkenes/O2 catalytic system. Notably, electron-deficient cyclic alkenes such as p-benzoquinones (BQs) and maleimides are key additives that facilitate nucleophilic attack of oxygen nucleophiles on coordinated terminal alkenes and enhance the AM selectivity. BQs also function to oxidize Pd(0) depending on the reaction conditions. Several other factors that improve the AM selectivity, such as the steric demand of the nucleo­philes, slow substrate addition, and halogen-directing groups, are also discussed.1 Introduction2 Anti-Markovnikov Oxidation of Aromatic Alkenes to Terminal Acetals­3 Anti-Markovnikov Oxidation of Aromatic Alkenes to Aldehydes4 Anti-Markovnikov Oxidation of Aliphatic Alkenes to Terminal Acetals­5 Anti-Markovnikov Oxidation of Aliphatic Alkenes to Aldehydes6 Conclusion

Direct use of allylic alcohols and allylic amines in palladium-catalyzed allylic amination

2017 ◽  
Vol 53 (37) ◽  
pp. 5151-5154 ◽  
Author(s):  
Jiangyan Jing ◽  
Xiaohong Huo ◽  
Jiefeng Shen ◽  
Jingke Fu ◽  
Qinghua Meng ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Functional Groups ◽  
Catalytic System ◽  
Allylic Alcohols ◽  
Allylic Amines ◽  
Allylic Amination ◽  
Reaction Conditions ◽  
Wide Range ◽  
Palladium Catalyzed ◽  
Direct Use

Allylic alcohols and allylic amines were directly utilized in a Pd-catalyzed hydrogen-bond-activated allylic amination under mild reaction conditions in the absence of any additives. The catalytic system is compatible with a variety of functional groups and can be used to prepare a wide range of linear allylic amines in good to excellent yields.

Suzuki–Miyaura cross-coupling for chemoproteomic applications

2020 ◽  
Author(s):  
Jian Cao ◽  
Ernest Armenta ◽  
Lisa Boatner ◽  
Heta Desai ◽  
Neil Chan ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Cross Coupling ◽  
Protein Profiling ◽  
Protein Labeling ◽  
Caspase 8 ◽  
Complex Cell ◽  
Bioorthogonal Chemistry ◽  
Reaction Conditions ◽  
Target Deconvolution ◽  
Palladium Catalyzed

Bioorthogonal chemistry is a mainstay of chemoproteomic sample preparation workflows. While numerous transformations are now available, chemoproteomic studies still rely overwhelmingly on copper-catalyzed azide –alkyne cycloaddition (CuAAC) or 'click' chemistry. Here we demonstrate that gel-based activity-based protein profiling (ABPP) and mass-spectrometry-based chemoproteomic profiling can be conducted using Suzuki–Miyaura cross-coupling. We identify reaction conditions that proceed in complex cell lysates and find that Suzuki –Miyaura cross-coupling and CuAAC yield comparable chemoproteomic coverage. Importantly, Suzuki–Miyaura is also compatible with chemoproteomic target deconvolution, as demonstrated using structurally matched probes tailored to react with the cysteine protease caspase-8. Uniquely enabled by the observed orthogonality of palladium-catalyzed cross-coupling and CuAAC, we combine both reactions to achieve dual protein labeling.

scholarly journals Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1651
Author(s):  
Felipe de la Cruz-Martínez ◽  
Marc Martínez de Sarasa Buchaca ◽  
Almudena del Campo-Balguerías ◽  
Juan Fernández-Baeza ◽  
Luis F. Sánchez-Barba ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Catalytic System ◽  
Phthalic Anhydride ◽  
Ring Opening ◽  
High Selectivity ◽  
Zinc Complexes ◽  
Cyclohexene Oxide ◽  
Reaction Conditions ◽  
Cyclic Anhydrides

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

Regiospecific Palladium-Catalyzed Cross-Coupling Reactions Using the Operational Equivalent of 1,3-Dilithiopropyne

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2387-2394 ◽  
Author(s):  
Jorge A. Cabezas ◽  
Natasha Ferllini
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Terminal Alkyne ◽  
Copper Iodide ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
High Yields

A regiospecific palladium-catalyzed cross-coupling reaction using the operational equivalent of the dianion 1,3-dilithiopropyne, with aromatic iodides is reported. This reaction gives high yields of 1-propyn-1-yl-benzenes and 2-(propyn-1-yl)thiophenes in the presence of catalytic amounts of palladium(0) or (II) and stoichiometric amounts of copper iodide. No terminal alkyne or allene isomers were detected. Reaction conditions were very mild and several functional groups were tolerated.

Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to Glyoxylates: Access to Optically Active Substituted Mandelic Acid Esters

Synlett ◽  
2019 ◽  
Vol 30 (14) ◽  
pp. 1693-1697
Author(s):  
Diao Chen ◽  
Jian-Guo Liu ◽  
Xu Zhang ◽  
Ming-Hua Xu
Keyword(s):  
Catalytic System ◽  
Mandelic Acid ◽  
Optically Active ◽  
Antiplatelet Drug ◽  
Reaction Conditions ◽  
Formal Synthesis ◽  
Arylboronic Acids ◽  
Synthetic Utility ◽  
Enantioselective Addition ◽  
Acid Esters

A rhodium-catalyzed enantioselective addition of glyoxylates to arylboronic acids promoted by a simple chiral sulfinamide-based olefin ligand under mild reaction conditions is described. The reaction provides access to a variety of optically active substituted mandelic acid esters in good yields with up to 83% ee. The catalytic system is also applicable to pyruvate addition. The synthetic utility of this method is highlighted by a formal synthesis of the antiplatelet drug clopidogrel.

Palladium-catalyzed highly regioselective hydroaminocarbonylation of aromatic alkenes to branched amides

2017 ◽  
Vol 15 (14) ◽  
pp. 2910-2913 ◽  
Author(s):  
Jinping Zhu ◽  
Bao Gao ◽  
Hanmin Huang
Keyword(s):  
Reaction Conditions ◽  
Efficient Catalyst ◽  
Palladium Catalyzed

Pd(t-Bu3P)2 has been successfully identified as an efficient catalyst for the hydroaminocarbonylation of aromatic alkenes to branched amides under relatively mild reaction conditions.

Palladium-catalyzed direct ortho-ethoxycarbonylation of azobenzenes and azoxybenzenes with diethyl azodicarboxylate

2015 ◽  
Vol 13 (34) ◽  
pp. 9083-9092 ◽  
Author(s):  
Ning Xu ◽  
Dengke Li ◽  
Yicheng Zhang ◽  
Lei Wang
Keyword(s):  
Reaction Conditions ◽  
Palladium Catalyzed ◽  
Diethyl Azodicarboxylate

A palladium-catalyzed direct ortho-ethoxycarbonylation of azobenzenes and azoxybenzenes with diethyl azodicarboxylate (DEAD) was developed under mild reaction conditions.

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