First Practical Asymmetric Synthesis of a New Tetrasubstituted
Tetrahydrofuran, (-)-Goniothalesdiol

Abstract

An efficient and practical strategy has been developed for the construction of the antipode of 3,4-dihydroxy-2,5-disubstituted tetrahydrofuran, goniothalesdiol, isolated from the bark of the Malaysian tree. The synthetic process is based on the convenient manipulation via Lewis acid-induced deoxygenation of the highly functionalized lactone derived from d-glucuronolactone.

Key words

goniothalesdiol - tetrasubstituted tetrahydrofuran - stereoselective deoxygenation - trisubstituted γ-lactone - d-glucuronolactone

References

• 1a Zeng L. Ye Q. Oberlies NH. Shi G. Gu Z.-M. He K. McLaughlin JL. Nat. Prod. Rep.  1996,  13:  275 
• 1b Cavé A. Figadère B. Laurens A. Cortes D. In Progress in the Chemistry of Organic Natural Products   Vol. 70:  Herz W. Springer-Verlag; Wien, New York: 1997.  p.81 
• 2a Bauer I. Maranda L. Young KA. Shimizu Y. Huang S. Tetrahedron Lett.  1995,  36:  7093 
• 2b Sakai R. Rinehart KL. J. Nat. Prod.  1995,  58:  773 
• 2c Wipf P. Lim S. J. Am. Chem. Soc.  1995,  117:  558 
• 3a Matsuo Y. Suzuki M. Masuda M. Chem. Lett.  1995,  1043 
• 3b Morte M. Tetrahedron Lett.  1997,  38:  3137 
• 3c Koert U. Angew. Chem., Int. Ed. Engl.  1995,  34:  298 
• 4 Faulkner DJ. Nat. Prod. Rep.  1997,  14:  259 
• 5 Seki T. Satake M. Mackenzie L. Kaspar HF. Yasumoto T. Tetrahedron Lett.  1995,  36:  7093 
• 6a Boukouvalas J. Fortier G. Radu I.-I. J. Org. Chem.  1998,  63:  916 
• 6b Fernández de la Pradilla R. Montero C. Priego J. Martínez-Cruz LA. J. Org. Chem.  1998,  63:  9612 
• 6c Capon RJ. Barrow RA. Skene C. Rochfort S. Tetrahedron Lett.  1997,  38:  7609 
• 6d Capon RJ. Barrow RA. J. Org. Chem.  1998,  63:  75 
• 6e Capon RJ. Barrow RA. Rochfort S. Jobling M. Skene C. Lacey E. Gill JH. Friedel T. Wadsworth D. Tetrahedron  1998,  54:  2227 
• 6f Wang Z.-M. Shen M. J. Org. Chem.  1998,  63:  1414 
• 6g Mori Y. Sawada T. Furukawa H. Tetrahedron Lett.  1999,  40:  731 ; and references cited therein
• 7a Stevens DR. Whiting DA. J. Chem. Soc., Perkin Trans. 1  1992,  633 
• 7b Mitra J. Mitra AK. J. Chem. Soc., Perkin Trans. 1  1992,  1285 
• 7c Maiti G. Adhikari S. Roy SC. J. Chem. Soc., Perkin Trans. 1  1995,  927 
• 7d Yoshida S.-I. Ogiku T. Ohmizu H. Iwasaki T. J. Org. Chem.  1997,  62:  1310 
• 7e Chen I.-S. Chen J.-J. Duh C.-Y. Tsai I.-L. Phytochemistry  1997,  45:  991 
• 8a Yoda H. Kimura K. Takabe K. Synlett  2001,  400 
• 8b Yoda H. Maruyama K. Takabe K. Tetrahedron: Asymmetry  2001,  12:  1403 
• 8c Yoda H. Mizutani M. Takabe K. Tetrahedron Lett.  1999,  40:  4701 
• 9 Cao S.-G. Wu X.-H. Sim K.-Y. Tan BKT. Pereira JT. Goh S.-H. Tetrahedron  1998,  54:  2143 
• 10a Geran RI. Greenberg NH. MacDonald MM. Schumacher AM. Abbott BJ. Cancer Chemother. Rep.  1972,  3:  1 
• 10b Talapatra SK. Basu D. Deb T. Goswani S. Talapatra B. Indian J. Chem., Sect. B  1985,  24:  29 
• 10c Mukai C. Hirai S. Hanaoka M. J. Org. Chem.  1997,  62:  6619 
• 10d Tsubuki M. Kanai K. Nagase H. Honda T. Tetrahedron  1999,  55:  2493 ; and references cited therein
• 11 Yoda H. Shimojo T. Takabe K. Synlett  1999,  1969 
• 12a Yoda H. Mizutani M. Takabe K. Heterocycles  1998,  48:  479 
• 12b Yoda H. Mizutani M. Takabe K. Synlett  1998,  855 
• 13a Lewis MD. Cha JK. Kishi Y. J. Am. Chem. Soc.  1982,  104:  4976 
• 13b Kraus GA. Molina MT. Walling JA. J. Org. Chem.  1987,  52:  1273 
• 13c Yoda H. Yamazaki H. Kawauchi M. Takabe K. Tetrahedron: Asymmetry  1995,  6:  2669 ; and references cited therein

14

The absolute S-configuration of the new asymmetric center in 5a was proved by the transformation into the meso compound 12 through sequential seven steps as shown below (Figure [2] ).

15

Coupling reaction of this diol intermediate 13 with Horner-Emmons reagent interestingly brought about the tricyclic compound 15 directly in 75% isolated yield as a sole product. It is reasonable to assume that the formation of 15 would be resulted in the reaction through intramolecular Michael addition followed by cyclization of α,β-unsaturated ester 14 (Figure [3] ).

16

Hydrogenation and simultaneous removal of the benzyl groups in 9 with Pd on carbon (10%) under H₂ atmosphere were proved to give a complex mixture. In addition, the hydrogenated final enantiomer of 1 was unstable and decomposed on standing.