Glycolaldehyde As A Bio-Based C-2 Platform Chemical: Catalytic Reductive Amination Of Vicinal Hydroxyl Aldehydes

Reductive amination of glycolaldehyde (GA), the smallest sugar molecule and obtainable from biomass, creates a versatile platform for ethylamine products, potentially replacing current pathways via toxic ethylene oxide and dichloroethane. Given the high reactivity of alpha-OH carbonyls, the main challenge was control of selectivity in a cascade of parallel and consecutive reactions during reductive amination. The type of solvent and catalyst, preferably methanol and Pd, respectively, are key enabling parameters to achieve high product yields. A kinetic study on product intermediates accompanied with detailed product analysis (MS and NMR) suggested a general mechanistic scheme and validation with density functional theory calculations provided a rational understanding of the solvent effect in terms of energetics and kinetics. Primary alkanolamines (AA) such as 2-(dimethylamino)-ethanol are preferred products, and large excess of the amine reagent is not required to reach almost quantitative yields. Interestingly substoichiometric amine-to-GA ratio allows for high yield of higher (consecutive) AAs such as N-methyldiethanolamine (MDEA) and triethanolamine, for which a peculiar cyclic 5-membered oxazolidinic precursor was analyzed (e.g., for reaction with monomethylamine to MDEA). The shift to diamine-selective (DA) reactions is possible by switching to a two-step one-pot approach. With ethylene glycol as a preferred solvent, high yield of an unsaturated C-2-enediamine precursor is obtained under an inert atmosphere, followed by its metal-catalyzed hydrogenation at elevated temperature to the final DA product such as N,N,N',N'-tetramethylethylene-diamine. A conceptual model of the catalytic reductive amination routes that allows production of a variety of ethylamines with up to +90 C % yield is thus presented. The successful preparation and sensory assessment of a GA-based diester quat in fabric softener formulations demonstrates the viability of a full bio-based and drop-in production route for high-value chemicals, directly from GA as a platform molecule.