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Current Organic Chemistry

Editor-in-Chief

ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

Spiroacetals in Insects

Author(s): W. Francke and W. Kitching

Volume 5, Issue 2, 2001

Page: [233 - 251] Pages: 19

DOI: 10.2174/1385272013375652

Price: $65

Abstract

Spiroacetals, cryptic ketodiols showing a hydroxyl group at both sides of a carbonyl whithin reachable distances are very widespread in nature. A group of 30 different structures, not including stereoisomers, represent volatile, less polar constituents of insect secretions.Five different systems were identified 1,6-dioxaspiro[ 4.4]nonanes, 1,6-dioxaspiro[4.5]decanes, 1,6-dioxaspiro[4.6]undecanes, 1,7-dioxaspiro[5.5]undecanes, and 1,7-dioxaspiro[5.6]dodecanes. Some spiroacetals are insect pheromones (2S,5R)-2-ethyl-1,6-dioxaspiro[4.4]nonane, chalcogran, 1, is a key component of the male produced aggregation pheromone of the spruce bark beetle, Pityogenes chalcographus. In contrast, (5S,7S)-7-methyl-1,6-dioxaspiro[4.5]decane, 2, conophthorin, acts as a repellent or spacer in several bark beetles. Racemic 1,7-dioxaspiro[5.5]undecane, olean, 5, is the female produced sex pheromone of the olive fly, Bactrocera (Dacus) oleae. The most widespread spiroacetal is 2,8-dimethyl-1,7-dioxaspiro[ 5.5]undecane, 8. It often forms a mixture of (E,E)- and (E,Z)-isomers, the (E,E)-isomer showing (2S,6R,8S)-configuration. In the solitary bee, Andrena wilkella, it serves as an aggregation pheromone. Present knowledge on structures and distribution of volatile spiroacetals is comprehensively compiled. Stereochemical aspects and mass spectrometric fragmentation patterns are discussed in detail to facilitate identifications of hitherto unknown compounds. Synthetic approaches to spiroacetals are classified and reviewed. Last but not least, facts and speculations on the biosynthesis of volatile spiroacetals are presented.

Keywords: cryptic ketodiols, dioxaspiro, pityogenes chalcographus, undecane, olean, spiroacetals, insect volatiles


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