Chemistry of Sugar Formation in the Gas Phase: Following the Activated Aldehyde.

Sugars are produced by living organisms, and are required building blocks for life as we know it, which raises the foundational question of how sugars formed in a prebiotic environment. The abiotic formose reaction produces sugars from formaldehyde, but our understanding of its initiation step remains murky, with chemists invoking the concept of an "activated aldehyde" to seed this reaction. Singlet hydroxycarbenes, high-energy isomers of aldehydes, were recently reported to facilitate sugar formation under cold, nonaqueous conditions relevant to interstellar environments. We generate singlet methylhydroxycarbene (1CH3-C̈-OH) from the photodissociation of pyruvic acid and experimentally measure its gas-phase reaction with d4-acetaldehyde using multiplexed photoionization mass spectrometry. The C4H4D4O2 isomer d4-acetoin is the sole product, which we kinetically link to the reactant CH3-C̈-OH, and attribute to a carbonyl-ene formation mechanism. We see no evidence of 3-hydroxybutanal, the C-H insertion product expected in carbene chemistry. Using automated exploration we calculate stationary points on the potential energy surface and report master equation rate coefficients from T = 20-600 K, providing quantitative kinetics of this fast reaction for use in chemical models. The prereactive complex in this reaction is stabilized by both hydrogen bonding and electrophilic carbene C═O interactions. These effects create a short-range dynamical bottleneck for the reaction besides the long- and midrange barrierless bottlenecks. Combined with recent reports of 1HC̈OH production from methanol photodissociation and pyruvic acid production in cold irradiated ices, this work provides evidence that singlet hydroxycarbene + aldehyde chemistry is a feasible path to prebiotic sugar formation.