Synthesis and structure revision of wasulfisides: glucosyl disulfides isolated from wasabi

The first syntheses of three natural glucosyl disulfides—wasulfisides A, B, and 3- epi -wasulfiside B—were successfully accomplished. These compounds were originally isolated from wasabi ( Eutrema japonicum ) and possess a rare natural β-glucosyl disulfide motif. The core structure was efficiently constructed via S–S bond formation between a β-glucosyl thiotosylate and various thiols. The overall yields reached 37%, starting from d -glucose. Accordingly, the structure of wasulfiside A, a unique oxadithiocine-containing compound, was successfully revised based on the syntheses of its regio- and stereoisomers. • Synthesis of Wasulfisides A, B, and 3- epi -wasulfiside B • Structure revision of Wasulfiside A • Efficient construction of glucosyl disulfides