Abstract

A catalytic reaction using syngas (CO/H2) as feedstock for the selective β-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)2Br[HN(C2H4PiPr2)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 sp3 carbon centers utilizing renewable feedstocks and energy for the synthesis of biologically active compounds, fine chemicals, and advanced biofuels.

Highlights

  • Background and motivationSynthesis gas, a mixture of carbon monoxide (CO) and hydrogen (H2), is a crucial relay between the energy and the chemical sector

  • A catalytic reaction using syngas (CO/H2) as feedstock for the selective b-methylation of alcohols was developed whereby carbon monoxide acts as a C1 source and hydrogen gas as a reducing agent

  • We report here a novel catalytic process using syngas to install methyl branches (H3C–) with high selectivity at existing aliphatic carbon chains in the b-position of alcohol substrates (Scheme 1)

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Summary

Introduction

Background and motivationSynthesis gas (syngas), a mixture of carbon monoxide (CO) and hydrogen (H2), is a crucial relay between the energy and the chemical sector. A catalytic reaction using syngas (CO/H2) as feedstock for the selective b-methylation of alcohols was developed whereby carbon monoxide acts as a C1 source and hydrogen gas as a reducing agent.

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