Development and Comparison of the Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols

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Abstract

Three catalysts for aerobic oxidation of alcohols are discussed and the effectiveness of each is evaluated for allylic, benzylic, aliphatic, and functionalized alcohols. Additionally, chiral nonracemic substrates as well as chemoselective and diastereoselective oxidations are investigated. In this study, the most convenient system for the Pd-catalyzed aerobic oxidation of alcohols is Pd(OAc)₂ in combination with triethylamine. This system functions effectively for the majority of alcohols tested and uses mild conditions (3 to 5 mol % of catalyst, room temperature). Pd(IiPr)(OAc)₂(H₂O) (1) also successfully oxidizes the majority of alcohols evaluated. This system has the advantage of significantly lowering catalyst loadings but requires higher temperatures (0.1 to 1 mol % of catalyst, 60 °C). A new catalyst is also disclosed, Pd(IiPr)(OPiv)₂ (2). This catalyst operates under very mild conditions (1 mol %, room temperature, and air as the O₂ source) but with a more limited substrate scope.

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This article has been cited by 32 ACS Journal articles (5 most recent appear below).

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    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
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  Synthesis and Structure of 1,4-Diphenyl-3-methyl-1,2,3-triazol-5-ylidene Palladium Complexes and Application in Catalytic Hydroarylation of Alkynes

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    An abnormal or mesoionic N-heterocyclic carbene (NHC), namely 1,4-diphenyl-3-methyl-1,2,3-triazol-5-ylidene (Tz), formed from 1,4-diphenyl-3-methyl-1,2,3-triazolium iodide and silver oxide, gave the corresponding silver carbene complex. The ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
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  Oxidatively Resistant Ligands for Palladium-Catalyzed Aerobic Alcohol Oxidation

  David M. Pearson, Nicholas R. Conley, and Robert M. Waymouth
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  • Oxidatively Resistant Ligands for Palladium-Catalyzed Aerobic Alcohol Oxidation

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    The complex [(neocuproine)Pd(OAc)]2[OTf]2 (1) catalyzes the aerobic oxidation of 2-heptanol at room temperature, but competitive ligand oxidation leads to low catalyst lifetimes. In an effort to mitigate the oxidative degradation of the ligand, a variety ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  (N-Heterocyclic Carbene)-Pd-Catalyzed Anaerobic Oxidation of Secondary Alcohols and Domino Oxidation−Arylation Reactions

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    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Homogeneous, Anaerobic (N-Heterocyclic Carbene)−Pd or −Ni Catalyzed Oxidation of Secondary Alcohols at Mild Temperatures

  Christophe Berini, Daniel F. Brayton, Corey Mocka and Oscar Navarro
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  • Homogeneous, Anaerobic (N-Heterocyclic Carbene)−Pd or −Ni Catalyzed Oxidation of Secondary Alcohols at Mild Temperatures

    Christophe Berini, Daniel F. Brayton, Corey Mocka and Oscar Navarro
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    The use of aryl chlorides as oxidants for the selective oxidation of a variety of secondary alcohols in anaerobic conditions with (NHC)−Pd and −Ni systems (NHC = N-heterocyclic carbene) at very mild temperatures is presented.

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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