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Oxidation-reductive coupling of alcohols catalyzed by oxo-vanadium complexes
Eric Steffensmeier1, Kenneth M Nicholas
1Department of Chemistry and Biochemistry, University of Oklahoma, 101 Stephenson Pkwy, Norman, OK 73019, USA. knicholas@ou.edu.
Chemical Communications (Cambridge, England)
|January 9, 2018
Summary
Oxo-vanadium complexes catalyze alcohol redox reactions, producing carbonyls and hydrocarbon dimers. This involves V-alkoxide intermediates that form carbon radicals, leading to dimer formation.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Benzylic and allylic alcohols are versatile organic substrates.
- Redox disproportionation offers a pathway for functional group transformation.
- Vanadium complexes are known catalysts for various organic reactions.
Purpose of the Study:
- To investigate the catalytic activity of oxo-vanadium complexes.
- To explore the redox disproportionation of benzylic and allylic alcohols.
- To elucidate the mechanism of co-product formation.
Main Methods:
- Experimental studies involving oxo-vanadium complexes.
- Catalytic reactions with benzylic and allylic alcohols.
- Computational chemistry to support mechanistic proposals.
Main Results:
- Oxo-vanadium complexes effectively catalyze the redox disproportionation.
- Carbonyl products and hydrocarbon dimers are co-produced.
- Evidence suggests reduced V-alkoxide intermediates are involved.
Conclusions:
- The catalytic system enables the synthesis of valuable carbonyl compounds and dimers.
- The mechanism involves C-O bond homolysis of V-alkoxide species.
- This pathway provides access to carbon free radicals for dimer formation.
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