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Optical resolution of rotenoids

Journal of Heterocyclic Chemistry

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DOI: 10.1002/jhet.5570240358

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Abstract

Optical resolution of selected rotenoids containing 1-3 asymmetric centers in dihydrobenzopyranofuroben-zopyranone and dihydrobisbenzopyranopyranone series has been achieved on two chiral high-performance liquid chromatographic (hplc) stationary phases. In most cases, the absolute stereochemistry at the cis-B/C ring junction of the rotenoidal antipodes can be related to their elution order. Generally, the 6aα,12aα-enantiomers were more strongly retained by the chiral substrate than their corresponding optical antipodes. The elution-configuration relationship provides potential utility for predicting the absolute configuration of related rotenoidal compounds. Chiral phase hplc on amino-acid-bonded-silica yielded results explicable in terms of Pirkle's bonding schemes for chiral recognition. Resolution data for 12a-hydroxy-, 12a-methoxy-, and 12-hydroxyiminorotenoids further corroborate the mechanistic rationale, and demonstrate that nonpolar π-π interactions appeared to be important for enantiomeric separation on helic poly-triphenylmethylacryl-ate-silica (CPOT). In the latter system, steric effects and conformational factors in association with the modification of E-ring structures might play significant roles in the chiral separation process in view of the reversal to the elution order observed for all methoxylated rotenoids and elliptone derivatives including the parent deguelin. The unique separability (α = 1.44) of 12a-hydroxyelliptone on CPOT was suggestive of structural effects of the 5-side chain on the resolution of the rotenoids having a five-membered-E-ring. The results obtained with two different types of chiral phases are complementary and useful for optical resolution of a wide variety of natural and synthetic rotenoidal compounds.

Additional Publication Details

Publication type:
Article
Publication Subtype:
Journal Article
Title:
Optical resolution of rotenoids
Series title:
Journal of Heterocyclic Chemistry
DOI:
10.1002/jhet.5570240358
Volume
24
Issue:
3
Year Published:
1987
Language:
English
Publisher:
Wiley
Publisher location:
Hoboken, NJ
Contributing office(s):
Upper Midwest Environmental Sciences Center
Description:
8 p.
Larger Work Type:
Article
Larger Work Subtype:
Journal Article
Larger Work Title:
Journal of Heterocyclic Chemistry
First page:
845
Last page:
852
Number of Pages:
8