Action of Molybdate Anion on d ‑Glucosone: Catalytic Conversion to Aldonates Involving C1–C2 Transposition
Year: 2024
Type: article
Abstract: Treatment of the osone (aldos-2-ulose), d-[1-13C]glucosone (11), with sodium molybdate at 90° for 30 h gave a mixture of d-[2-13C]gluconate (22) and d-[2-13C]mannonate (32) in an 85:15 ratio, indicating that the reaction proceeds with C1–C2 transposition similar to that observed previously with aldoses. Reactions with several singly and doubly 13C-labeled isotopomers of 1 confirmed this transposition. In contrast to the aldose reaction, the reaction with 1 is irreversible, presumably due to electrostatic repulsion between the negatively charged catalytically active bimolybdate species and the negatively charged aldonate product. The production of 2 and 3 is mediated by the formation of two structurally distinct bimolybdate complexes, one producing the gluco isomer and the other producing the manno isomer. Reaction byproducts were also observed, specifically d-[1-13C]arabinose (41) and [13C]formate (5), when 11 was used as the reactant. These byproducts appear to form from the breakdown of bimolybdate complexes via alternative pathways that compete with those responsible for aldonate formation.
Source: ACS Omega
Authors: Wenhui Zhang, Anthony S. Serianni
Institution: University of Notre Dame
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $1,935
OpenAlex ID: W4402634342