Vicinal Tetrahydrofuranyl Substitution of Alkyl Chains. Tetra-, Penta-, and Hexafunctionalized Arrays

The tetrakis (tetrahydrofuranyl) dialdehydes 14 and 19 are accessible by oxidative cleavage of extensively substituted cyclohexenes, which have in turn been assembled in a stereocontrolled manner. Reaction of 14 with an excess of the Normant reagent followed by ring closure resulted in conversion to...

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Bibliographic Details
Published in:Journal of organic chemistry 2000-07, Vol.65 (14), p.4303-4308
Main Authors: Paquette, Leo A, Ohmori, Naoki, Lowinger, Timothy B, Rogers, Robin D
Format: Article
Language:English
Subjects:
Aldehydes - chemical synthesis
Aldehydes - chemistry
Alkylation
Cyclohexanes - chemistry
Cyclohexenes
Models, Molecular
Molecular Conformation
Molecular Structure
Stereoisomerism
Structure-Activity Relationship
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Summary:The tetrakis (tetrahydrofuranyl) dialdehydes 14 and 19 are accessible by oxidative cleavage of extensively substituted cyclohexenes, which have in turn been assembled in a stereocontrolled manner. Reaction of 14 with an excess of the Normant reagent followed by ring closure resulted in conversion to the hexafunctionalized polyether 15. Allylindation of the same dialdehyde gave rise to lactol 16, a reactivity pattern that was essentially duplicated when 19 was treated with the Normant reagent. Attempts to add allylmagnesium bromide to 19 resulted in operation of a Tishchenko reaction with formation of lactone 23. By means of X-ray diffraction analysis, it was possible to ascertain the conformation adopted by 20 and 23 in the solid state. In addition, 15 was shown to populate a conformation in which the oxygen are very predominantly in gauche arrangements, this structural preorganization taking place in the absence of any metal ions.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0001075