Green Chemistry for Catalytic C-C Coupling of Renewable Feedstocks

• Applicant: Professor Dr. Bernhard Breit
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2010 to 2015
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 181737472

• Final Report Year: 2017

Final Report Abstract

Beyond Hydroformylation. Ruthenium catalyzed reductive couplings of paraformaldehyde to dienes, alkynes and allenes provide access to products of hydrohydroxymethylation that cannot be formed selectively under the conditions of hydroformylation. In certain cases, using nickel catalysts, the regioselectivity of C-C coupling can be inverted. Using iridium catalysts, methanol engages in redox-neutral regioselective hydrohydroxymethylation.

Publications

• “Divergent Regioselectivity in the Synthesis of Trisubstituted Allylic Alcohols by Nickel- and Ruthenium-Catalyzed Alkyne Hydrohydroxymethylation with Formaldehyde”. Angew. Chem. 2011, 123, 5805-5808; Angew. Chem. Int. Ed. 2011, 50, 5687-5690
  C. C. Bausch, R. L. Patman, B. Breit, M. J. Krische
  
• “Regiodivergent reductive coupling of 2-substituted dienes to formaldehyde employing ruthenium or nickel catalyst: hydrohydroxymethylation via transfer hydrogenation”. Chem. Sci. 2013, 4, 1876-1880
  A. Köpfer, B. Sam, B. Breit, M. Krische
  (See online at https://doi.org/10.1039/c3sc22051f)
• “Paraformaldehyde and Methanol as C1 Feedstocks in Metal-Catalyzed C-C Couplings of π-Unsaturated Reactants: Beyond Hydroformylation”. Angew. Chem. 2015, 127, 3317-3325; Angew. Chem. Int. Ed. 2015, 54, 3267-3274
  B. Sam, B. Breit, M. J. Krische
  (See online at https://doi.org/10.1002/anie.201407888)