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.

scholarly journals Bis-NHC–Ag/Pd(OAc)2 Catalytic System Catalyzed Transfer Hydrogenation Reaction

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 8
Author(s):  
Hui-Ju Chen ◽  
Chien-Cheng Chiu ◽  
Tsui Wang ◽  
Dong-Sheng Lee ◽  
Ta-Jung Lu
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
High Efficiency ◽  
Aqueous Media ◽  
Hydrogenation Reaction ◽  
Transfer Hydrogenation ◽  
Terminal Alkynes ◽  
Wide Range ◽  
Transfer Hydrogenation Reaction

The bis-NHC–Ag/Pd(OAc)2 catalytic system (NHC = N-heterocyclic carbene), a combination of bis-NHC–Ag complex and Pd(OAc)2, was found to be a smart catalyst in the Pd-catalyzed transfer hydrogenation of various functionalized arenes and internal/terminal alkynes. The catalytic system demonstrated high efficiency for the reduction of a wide range of various functional groups such as carbonyls, alkynes, olefins, and nitro groups in good to excellent yields and high chemoselectivity for the reduction of functional groups. In addition, the protocol was successfully exploited to stereoselectivity for the transformation of alkynes to alkenes in aqueous media under air. This methodology successfully provided an alternative useful protocol for reducing various functional groups and a simple operational protocol for transfer hydrogenation.

scholarly journals Palladium-Catalyzed [3+2] Cycloaddition via Two-Fold 1,3-C(sp3)−H Activation

2020 ◽  
Author(s):  
Hojoon Park ◽  
jin-quan yu
Keyword(s):  
Functional Groups ◽  
Sulfonic Acid ◽  
Cycloaddition Reaction ◽  
Wide Range ◽  
Leaving Group ◽  
Palladium Catalyzed ◽  
Directing Group ◽  
Overall Efficiency ◽  
Weak Coordination ◽  
Single Reaction

<div>Cycloaddition reactions provide an expeditious route to construct ring systems in a highly convergent and stereoselective manner. For a typical cycloaddition reaction to occur, however, the installation of multiple reactive functional groups (π-bonds, leaving group, etc.) are required within the substrates, compromising the overall efficiency or scope of the cycloaddition reaction. Here, we report a palladium-catalyzed [3+2] reaction that utilizes C(sp<sup>3</sup>)–H activation to generate the three-carbon unit for formal cycloaddition with maleimides. We implemented a strategy where the initial C(sp<sup>3</sup>)–H activation/olefin insertion would trigger a relayed, second remote C(sp<sup>3</sup>)–H activation to complete a formal [3+2] cycloaddition. The diastereoselectivity profile of this reaction resembles that of a typical pericyclic cycloaddition reaction in that the relationships between multiple stereocenters are exquisitely controlled in a single reaction. The key to success was the use of weakly coordinating amides as the directing group, as undesired Heck or alkylation pathways were preferred with other types of directing groups. The use of the pyridine-3-sulfonic acid ligands is critical to enable C(sp<sup>3</sup>)–H activation directed by this weak coordination. The method is compatible with a wide range of amide substrates, including lactams, which lead to novel spiro-bicyclic products. The [3+2] product is also shown to undergo a reductive desymmetrization process to access chiral cyclopentane bearing multiple stereocenters with excellent enantioselectivity.</div>

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

Regioselective Synthesis of Optically Active Trifluoromethyl Group Substituted Allylic Amines by Palladium-Catalyzed Allylic Amination

Synlett ◽  
2010 ◽  
Vol 2010 (19) ◽  
pp. 2887-2890 ◽  
Author(s):  
Motoi Kawatsura ◽  
Toshiyuki Itoh ◽  
Takuya Hirakawa ◽  
Kazunori Ikeda ◽  
Hiroshi Ogasa
Keyword(s):  
Optically Active ◽  
Regioselective Synthesis ◽  
Trifluoromethyl Group ◽  
Allylic Amines ◽  
Allylic Amination ◽  
Palladium Catalyzed

Regioselective synthesis of trifluoromethyl group substituted allylic amines via palladium-catalyzed allylic amination

2008 ◽  
Vol 49 (15) ◽  
pp. 2450-2453 ◽  
Author(s):  
Motoi Kawatsura ◽  
Takuya Hirakawa ◽  
Tomoko Tanaka ◽  
Daiji Ikeda ◽  
Shuichi Hayase ◽  
...  
Keyword(s):  
Regioselective Synthesis ◽  
Trifluoromethyl Group ◽  
Allylic Amines ◽  
Allylic Amination ◽  
Palladium Catalyzed

scholarly journals Nickel-Catalyzed Reductive Coupling of Unactivated Alkyl Bromides and Aliphatic Aldehydes

2021 ◽  
Author(s):  
Cole Cruz ◽  
John Montgomery
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
Cross Coupling ◽  
Secondary Alcohols ◽  
Reductive Coupling ◽  
Aliphatic Aldehydes ◽  
Alkyl Bromide ◽  
Alkyl Bromides ◽  
Wide Range ◽  
Ni Species

We report the development of a mild, convenient coupling of aliphatic aldehydes and unactivated alkyl bromides. The catalytic system features the use of a common Ni(II) precatalyst and a readily available bisoxazoline ligand and affords silyl-protected secondary alcohols. The reaction is operationally simple, utilizing Mn as a stoichiometric reductant, and tolerates a wide range of functional groups. Initial mechanistic experiments support a mechanism featuring an alpha-silyloxy Ni species which undergoes formal oxidative addition of the alkyl bromide species via a reductive cross-coupling pathway.

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.

scholarly journals Highly enantioselective isomerization of primary allylic alcohols catalyzed by (P,N)-iridium complexes

2010 ◽  
Vol 82 (7) ◽  
pp. 1461-1469 ◽  
Author(s):  
Luca Mantilli ◽  
David Gérard ◽  
Sonya Torche ◽  
Céline Besnard ◽  
Clément Mazet
Keyword(s):  
Asymmetric Catalysis ◽  
Organic Synthesis ◽  
Industrial Application ◽  
Allylic Alcohols ◽  
Iridium Complexes ◽  
Allylic Amines ◽  
Reaction Conditions ◽  
Significant Challenge ◽  
Catalytic Asymmetric

The catalytic asymmetric isomerization of allylic amines to enamines stands out as one of the most accomplished and well-studied reactions in asymmetric catalysis as illustrated by its industrial application. In contrast, the related asymmetric isomerization of primary allylic alcohols to the corresponding aldehydes still constitutes a significant challenge in organic synthesis. Herein, we show that under appropriate reaction conditions, iridium-hydride catalysts promote the isomerization of primary allylic alcohols under very mild reaction conditions. The best catalysts deliver the desired chiral aldehydes with unprecedented levels of enantioselectivity and good yields. Mechanistic hypotheses have been drawn based on preliminary investigations.

Hydrogen-Bond-Assisted Activation of Allylic Alcohols for Palladium-Catalyzed Coupling Reactions

ChemSusChem ◽  
2014 ◽  
Vol 7 (3) ◽  
pp. 890-896 ◽  
Author(s):  
Yasemin Gumrukcu ◽  
Bas de Bruin ◽  
Joost N. H. Reek
Keyword(s):  
Hydrogen Bond ◽  
Allylic Alcohols ◽  
Coupling Reactions ◽  
Palladium Catalyzed
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