Ruthenium Pincer‐Catalyzed Cross‐Dehydrogenative Coupling of Primary Alcohols with Secondary Alcohols under Neutral Conditions

@article{Srimani2012RutheniumPC,
  title={Ruthenium Pincer‐Catalyzed Cross‐Dehydrogenative Coupling of Primary Alcohols with Secondary Alcohols under Neutral Conditions},
  author={Dipankar Srimani and Ekambaram Balaraman and Boopathy Gnanaprakasam and Yehoshoa Ben‐David and David Milstein},
  journal={Advanced Synthesis \& Catalysis},
  year={2012},
  volume={354},
  pages={2403-2406}
}
Cross-dehydrogenative coupling of primary alcohols with secondary alcohols to obtain mixed esters with the liberation of molecular hydrogen is achieved in high yield and good selectivity under neutral conditions, using a bipyridyl-based PNN ruthenium(II) pincer catalyst. 
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95 Citations

95 Citations

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Citation Type

Ruthenium Pincer-Catalyzed Cross-Dehydrogenative Coupling of Primary Alcohols with Secondary Alcohols under Neutral Conditions.
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References

SHOWING 1-10 OF 44 REFERENCES
Ruthenium Pincer-Catalyzed Acylation of Alcohols Using Esters with Liberation of Hydrogen under Neutral Conditions
Acylation of secondary alcohols using non-activated esters, in particular symmetrical esters (such as ethyl acetate), is achieved under neutral conditions with the liberation of molecular hydrogen.…
Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex
The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with…
Direct β-Alkylation of Secondary Alcohols with Primary Alcohols Catalyzed by a Cp*Ir Complex
A new catalytic system for β-alkylation of secondary alcohols has been developed. In the presence of [Cp*IrCl2]2 (Cp* = pentamethylcyclopentadienyl) catalyst and base, the reactions of various…
Catalyzed dehydrogenative coupling of primary alcohols with water, methanol, or amines.
TLDR
The multistep mechanism was elucidated by computational methods and metal-ligand cooperativity is responsible for the high activity of the rhodium amido complex 1 in the dehydrogenative coupling of primary alcohols with water, methanol, or amines to give carboxylic acids, methyl carboxylates, oramides, respectively.
Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes
An efficient, environmentally benign method for the preparation of esters from alcohols under mild, neutral conditions without the need for carboxylic acid derivatives and condensing agents was…
Chemoselective nucleophilic arylation and single-step oxidative esterification of aldehydes using siloxanes and a palladium-phosphinous acid as a reaction switch.
Aldehydes and siloxanes form methyl esters in a single step through mild oxidative esterification in the presence of a palladium catalyst or, alternatively, afford secondary alcohols via…
Dehydrogenation of alcohols under ambient atmosphere by a recyclable sol–gel encaged iridium pincer catalyst
From esters to alcohols and back with ruthenium and osmium catalysts.
TLDR
The Os dimer is an outstanding catalyst for the hydrogenation of alkenoates and triglycerides, and allows production of fatty alcohols from olive oil.
Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst
Methyl esters can be produced in high yields by oxiding methanolic solutions of primary alcohols with dioxygen over a heterogeneous gold catalyst. The versatility of this new methodology is…
Iron-Catalyzed One-Pot Oxidative Esterification of Aldehydes
A highly efficient, mild, and simple protocol for Fe(ClO4)3·xH2O-catalyzed oxidative esterification of aldehydes was developed. Several aromatic and aliphatic aldehydes reacted with simple primary…
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