Synthesis of 6-Hydroxymethylpterin α- and β-D-Glucosides

Synthesis of biopterin and related pterin glycosides

“…Using the key glycosyl acceptor 1′‐ O ‐PMB‐biopterin and ciliapterin derivatives ( 10 , 21 ), a novel, effective way for selective preparation of both pterin 2′‐ O ‐β‐ and 2′‐ O ‐α‐glycosides has been developed, as exemplified by the first synthesis of biopterin α‐ D ‐glucoside ( 1b ) (from 10 with the novel glycosyl donor 32 ) and limipterin ( 1d ) (from 10 with the glycosyl donor 19 ). Besides biopterin glycosides, these synthetic methodologies have been applied to glycoside syntheses of other pterins such as ciliapterin ( 2a ), neopterin ( 3a ), 6‐hydroxymethylpterin ( 4a ) (48), and 6‐hydroxymethylisoxanthopterin ( 6a ). The NMR data of the synthetic pterin glycosides have proved to be essentially identical with those reported for the natural products, thus validating their proposed structures.…”

First Synthesis of a Natural Neopterin Glycoside: 3'-O-(β-D-Glucopyranosyluronic acid)neopterin

“…in dichloromethane at room temperature for 2.5 h resulted in the predominant formation of the 1',2',3'-tri-Oacetylneopterin derivative (13) in 53% yield; the desired 3'-O-(β-D-glucopyranosyluronate)neopterin derivative (12) was obtained in a minor portion (31% yield). Production of 13 can be perceived as the result of the subtraction of 2-O-acetyl group of 11a by 10a via the α-D-glucopyranosulonate-1,2-orthoacetate intermediate (31). Similar treatment of 10a with 3.0 mol equiv.…”

“…By contrast, the functional roles of pterin glycosides have remaind obscure, though some inhibitory activities against tyrosinase were reported for biopterin D-glucoside (2) (23). Despite a considerable interest from the viewpoint of their biological activities and functions as well as the structural proof of hitherto reported natural products, attempts at preparation of natural pterin glycosides have so far scarcely been made, except for our synthetic studies on biopterin and ciliapterin glycosides (24)(25)(26)(27)(28)(29)(30)(31). We describe herein an efficient synthesis of 3'-O-(β-D-glucopyranosyluronic acid)neopterin (6) as the first synthetic example of a natural neopterin glycoside.…”