Synlett 2002(9): 1532-1534
DOI: 10.1055/s-2002-33531
LETTER
© Georg Thieme Verlag Stuttgart · New York

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

Hidemi Yoda*, Yuka Nakaseko, Kunihiko Takabe
Department of Molecular Science, Faculty of Engineering, Shizuoka University, Johoku 3-5-1, Hamamatsu 432-8561, Japan
Fax: +81(53)4781150; e-Mail: tchyoda@ipc.shizuoka.ac.jp;
Further Information

Publication History

Received 11 July 2002
Publication Date:
17 September 2002 (online)

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.

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.