Syntheses of Gabosine A, B, D, and E from Allyl Sulfide Derived from(-)-Quinic Acid

Abstract

An efficient conversion of allyl sulfide 6 prepared from (-)-quinic acid (5) to gabosines was achieved by a series of sequential reactions: i) Mislow-Evans rearrangement, ii) SeO₂ oxidation, iii) conjugate addition of sodium hydroxide or sodium acetate, and iv) elimination of the methoxymethyloxy group.

Key words

gabosine - cyclitol - allyl sulfide - quinic acid - conjugate addition

References

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• 3b

  The allyl sulfide can be prepared in a large scale (>20 g) from (-)-quinic acid via tributylphosphine-diphenyl disulfide-assisted regioselective dehydration and phenylthiolation of an exomethylene 1,2-diol intermediate.

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6

The exclusive diastereofacial rearrangement would be induced by the steric repulsion of the bulky allylic silyloxy group which lies on the α-face of the cyclohexane ring.

7

Structures of 9, 11a, and 11b were confirmed by their conversions into conduritols A and C. Full details of these results will be reported in due course.

10

Yields on the deprotection step to gabosines were good to moderate (>59%) due probably to the prolonged reaction period leading to the undesired acid-catalyzed decomposition.