Lasonolide A: Synthesis of A and B Rings via a Cycloetherification Strategy

Abstract

Syntheses of tetrahydropyrans ent-2 and ent-3, substructures of the A and B rings of the enantiomer of lasonolide A (1), are described. The syntheses of ent-2 and ent-3 feature highly stereo­selective cycloetherification reactions of bis-homoallylic alcohols 7 and 8.

Key words

tetrahydropyran - cycloetherification - phenylselenenyl chloride - lasonolide A - macrolide

References

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19

We thank Professor Lee for providing us with copies of ¹H and ¹³C NMR spectra of 2 and 3.

27

We thank Dr. Judith C. Gallucci for determining the structure of 40 at the OSU Chemistry Department Crystallographic Facility.

28

During the course of this work we have examined cyclizations of several structures related to 8 (replace C₆
p-methoxystyryl group with phenyl, 2-furyl, styryl). In all cases the structure corresponding to 35 was the major product in 60-70% yield. In one case (styryl) a minor diastereomer (5%) was detected in which all substituents were equatorially disposed on the tetrahydropyran ring with the exception of the benzyloxymethyl group (axially disposed).

33

Some of the reagents used in Schemes [1] and [2] are toxic (for example PhSeCl). Appropriate care should be used in the handling and disposal of these materials.