Studies Directed Towards the Biosynthesis of the C7N Unit of Rifamycin B: A New Synthesis of Quinic Acid from Shikimic Acid

Abstract
The synthesis of quinic acid (4) via epoxide 13, starting from shikimic acid (5), is described (Scheme 1). Treatment of 13 with thiophenol yielded not only 17, but also the γ‐lactones 18 and 19 as result of migration of silyl groups within a cis‐ and trans‐diol system. The conversion provides a direct stereoselective epoxidation of a shikimic‐acid derivative as well as an alternative pathway for the preparation of 4. A shorter approach via the disilylated epoxide 22 was unsuccessful because the γ‐lactone 25 was obtained in place of the desired α‐hydroxy ester 24 (Scheme 2).

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