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DOI: 10.1055/s-2002-32985
Syntheses of Gabosine A, B, D, and E from Allyl Sulfide Derived from(-)-Quinic Acid
Publication History
Publication Date:
25 July 2002 (online)
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
- Isolation and biological activity of gabosines:
- 1a
Tatsuta K.Tsuchiya T.Mikami N.Umezawa S.Umezawa H. J. Antibiot. 1974, 27: 579 - 1b
Muller A.Keller-Schierlein W.Bielecki J.Rak G.Stumpfel J.Zahner H. Helv. Chim. Acta 1986, 69: 1829 - 1c
Bach G.Breiding-Mack S.Grabley S.Hammann P.Hutter K.Thiericke R.Hermann U.Wink J.Zeeck A. Liebigs Ann. Chem. 1993, 241 - 1d
Tang Y.-Q.Maul C.Hofs R.Sattler I.Grabley S.Feng X.-Z.Zeeck A.Thiericke R. Eur. J. Org. Chem. 2000, 149 - For recent synthetic studies:
- 2a
Tatsuta K.Yasuda S.Araki N.Takahashi M.Kamiya Y. Tetrahedron Lett. 1998, 39: 401 - 2b
Lubineau A.Billaut I. J. Org. Chem. 1998, 63: 5668 - 2c
Frederick C.Huntley M.Wood HB.Ganem B. Tetrahedron Lett. 2000, 41: 2031 - 2d
Mehta G.Lakshminath S. Tetrahedron Lett. 2000, 41: 3509 - 3a
Shinada T.Yoshida Y.Ohfune Y. Tetrahedron Lett. 1998, 39: 6027 - 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.
- 4 For a review:
Evans DA.Andrews GC. Acc. Chem. Res. 1974, 7: 147 - 5 It was presumed that the allylic
oxidation of A would facilitate its conversion
to B in comparison with that from 6 or 8 according
to the related example:
Bamba M.Nishikawa T.Isobe M. Synlett 1998, 371 - 8
Kiegiel J.Wovkulich PM.Uskokovic MR. Tetrahedron Lett. 1991, 32: 6057 - 9
Albright JD.Goldman L. J. Am. Chem. Soc. 1967, 89: 2416
References
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.
7Structures 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.
10Yields 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.