Question

10. Isolation of a pure sample of the third product, which has been determined to be an isomer of the major and minor products, gives the following 13C NMR data. Determine the structure of this product. 2 points

Answer 1

Answer:

Four possible isomers (1–4) for the natural product essramycin. The structure of compound 1 was attributed to essramycin by 1H NMR, 13C NMR, HMBC, HRMS, and IR experiments.

Explanation:

Three synthetic routes were used to prepare all four compounds (Figure 2A). All three reactions utilize 2-(5-amino-4H-1,2,4-triazol-3-yl)-1-phenylethanone (5) as the precursor, whereas each uses different esters (6–8) to construct the pyrimidinone ring. Isomer 1 was prepared by reaction A, which used triazole 5 and ethyl acetoacetate (6) in acetic acid. This was the reaction used in syntheses of essramycin by the Cooper and Moody laboratories.3,4 Reaction B produced compound 2 (minor product) and compound 3 (major product), which were separated chromatographically. This reaction allowed reagent 5 to react with ethyl 3-ethoxy-2-butenoate (7) in the presence of sodium in methanol, under reflux for 24 h. Compound 4 was prepared by reaction C, which was obtained by reflux of 5 and methyl 2-butynoate (8) in n-butanol.