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Manganese(I)-Catalyzed ?-Methylation of Alcohols Using Methanol as C1 Source.

ABSTRACT: Highly selective ?-methylation of alcohols was achieved using an earth-abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)2 Br[HN(C2 H4 Pi Pr2 )2 ]] 1 ([HN(C2 H4 Pi Pr2 )2 ]=MACHO-i Pr). The reaction requires only low loadings of 1 (0.5?mol?%), methanolate as base and MeOH as methylation reagent as well as solvent. Various alcohols were ?-methylated with very good selectivity (>99?%) and excellent yield (up to 94?%). Biomass derived aliphatic alcohols and diols were also selectively methylated on the ?-position, opening a pathway to "biohybrid" molecules constructed entirely from non-fossil carbon. Mechanistic studies indicate that the reaction proceeds through a borrowing hydrogen pathway involving metal-ligand cooperation at the Mn-pincer complex. This transformation provides a convenient, economical, and environmentally benign pathway for the selective C-C bond formation with potential applications for the preparation of advanced biofuels, fine chemicals, and biologically active molecules.

SUBMITTER: Kaithal A 

PROVIDER: S-EPMC6973237 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Manganese(I)-Catalyzed β-Methylation of Alcohols Using Methanol as C<sub>1</sub> Source.

Kaithal Akash A   van Bonn Pit P   Hölscher Markus M   Leitner Walter W  

Angewandte Chemie (International ed. in English) 20191128 1

Highly selective β-methylation of alcohols was achieved using an earth-abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)<sub>2</sub> Br[HN(C<sub>2</sub> H<sub>4</sub> P<sup>i</sup> Pr<sub>2</sub> )<sub>2</sub> ]] 1 ([HN(C<sub>2</sub> H<sub>4</sub> P<sup>i</sup> Pr<sub>2</sub> )<sub>2</sub> ]=MACHO-<sup>i</sup> Pr). The reaction requires only low loadings of 1 (0.5 mol %), methanolate as base and MeOH as methylation reagent as well as solvent. Various alcoh  ...[more]

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