Alkyl Formates as Transfer Hydroalkylation Reagents and Their Use in the Catalytic Conversion of Imines to Alkylamines**

Abstract

Easily accessible via a simple esterification of alcohols with formic acid, alkyl formates are used as a novel class of transfer hydroalkylation reagents, CO2 acting as a traceless linker. As a proof‐of‐concept, their reactivity in the transfer hydroalkylation of imines is investigated, using a ruthenium‐based catalyst and LiI as promoter to cleave the C−O σ‐bond of the formate scaffold. Providing tertiary amines, the reaction displays a divergent regioselectivity compared to previously reported transfer hydroalkylation strategies.

Production of Methane by Catalytic Decarboxylation of Methyl Formate as a Liquid Surrogate

“…In order to improve the efficiency and the selectivity, we considered a plausible mechanism with intertwined catalytic cycles that involve: (i) facilitating the cleavage of the C−O bond of methyl formate by nucleophilic substitution, using lithium iodide, to form methyl iodide and lithium formate, (ii) decarboxylating the formate on the catalyst to form a metal hydride intermediate, and (iii) transferring this hydride equivalent to methyl iodide, yielding methane (Scheme 3). 61 First, a screening of catalysts was performed, using four ruthenium complexes known for their ability to form hydride species and/or perform decarboxylation reactions. 62,63 The decarboxylation of methyl formate was first tested with 3 mol % of [(MACHO)RuH(CO)Cl] 1, efficient in the transfer hydrogenation of esters.…”

Production of Methane by Catalytic Decarboxylation of Methyl Formate as a Liquid Surrogate

“…20 https://doi.org/10.26434/chemrxiv-2023-bkgd3 ORCID: https://orcid.org/0000-0002-0017-5500 Content not peer-reviewed by ChemRxiv. License: CC BY 4.0…”