Electronic and Nuclear Magnetic Resonance Spectroscopic Features of the 1‘,4‘-Iminopyrimidine Tautomeric Form of Thiamin Diphosphate, a Novel Intermediate on Enzymes Requiring This Coenzyme

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Abstract
Appropriate compounds were synthesized to create models for the 1‘,4‘-imino tautomer of the 4‘-aminopyrimidine ring of thiamin diphosphate recently found to exist on the pathway of enzymatic reactions requiring this cofactor [Jordan, F., and Nemeria, N. S. (2005) Bioorg. Chem.33, 190−215]. The N1-methyl-4-aminopyrimidinium compounds synthesized on treatment with a strong base produce the 1,4-imino tautomer whose UV spectrum indicates a maximum between 300 and 320 nm, depending on the absence or presence of a methyl group at the 4-amino nitrogen. The λmax found is in the same wavelength range as the positive circular dichroism band observed on several enzymes and showed a very strong dependence on solvent dielectric constant. To help with the 15N chemical shift assignments, the model compounds were specifically labeled with 15N at the amino nitrogen atom. The chemical shift of the amino nitrogen was deshielded by N1-methylation and then dramatically further deshielded by more than 100 ppm on formation of the 1,4-iminopyrimidine tautomer. Both the UV spectroscopic values and the 15N chemical shift for the 1,4-iminopyrimidine tautomer should serve as useful guides to the assignment of enzyme-bound signals.

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