4.8 Article

Carbon monoxide and hydrogen (syngas) as a C1-building block for selective catalytic methylation

Journal

CHEMICAL SCIENCE
Volume 12, Issue 3, Pages 976-982

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d0sc05404f

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Funding

  1. Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy-Exzellenzcluster 2186, The Fuel Science Center [390919832]
  2. Erasmus Mundus Action 1 Programme SINCHEM [FPA2013-0037]

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A catalytic reaction using syngas as feedstock for the selective beta-methylation of alcohols was developed, with carbon monoxide and hydrogen gas as key components. The complex molecular structure involving earth-abundant manganese enables the generation of formaldehyde from syngas. This new syngas conversion method provides a pathway for installing methyl branches at carbon centers and synthesizing biologically active compounds, fine chemicals, and advanced biofuels.
A catalytic reaction using syngas (CO/H-2) as feedstock for the selective beta-methylation of alcohols was developed whereby carbon monoxide acts as a C1 source and hydrogen gas as a reducing agent. The overall transformation occurs through an intricate network of metal-catalyzed and base-mediated reactions. The molecular complex [Mn(CO)(2)Br[HN((C2H4PPr2)-Pr-i)(2)]] 1 comprising earth-abundant manganese acts as the metal component in the catalytic system enabling the generation of formaldehyde from syngas in a synthetically useful reaction. This new syngas conversion opens pathways to install methyl branches at sp(3) carbon centers utilizing renewable feedstocks and energy for the synthesis of biologically active compounds, fine chemicals, and advanced biofuels.

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