Spiroacetals in insects

被引:151
作者
Francke, W
Kitching, W
机构
[1] Univ Hamburg, Inst Organ Chem, D-20146 Hamburg, Germany
[2] Univ Queensland, Dept Chem, Brisbane, Qld, Australia
关键词
D O I
10.2174/1385272013375652
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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-dioxaspirol[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 cha2cographus. 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-diosaspiro[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. Tt 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.
引用
收藏
页码:233 / 251
页数:19
相关论文
共 152 条
[1]   A SIMPLE ROUTE TO SPIROKETALS VIA ALKYLATION OF DIHYDROPYRAN [J].
AMOUROUX, R .
HETEROCYCLES, 1984, 22 (07) :1489-1492
[2]  
[Anonymous], 1993, SCENT ORCHIDS
[3]   ISOLATION AND SYNTHESIS OF 1,7-DIOXASPIRO[5.5]UNDECANE AND 1,7-DIOXASPIRO-[5.5]UNDECAN-3-AND -4-OLS FROM THE OLIVE FLY (DACUS-OLEAE) [J].
BAKER, R ;
HERBERT, RH .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1987, (05) :1123-1127
[4]   THE IDENTIFICATION OF SPIROACETALS IN THE VOLATILE SECRETIONS OF 2 SPECIES OF FRUIT-FLY (DACUS-DORSALIS, DACUS-CUCURBITAE) [J].
BAKER, R ;
BACON, AJ .
EXPERIENTIA, 1985, 41 (11) :1484-1485
[5]   IDENTIFICATION AND SYNTHESIS OF THE MAJOR SEX-PHEROMONE OF THE OLIVE FLY (DACUS-OLEAE) [J].
BAKER, R ;
HERBERT, R ;
HOWSE, PE ;
JONES, OT ;
FRANCKE, W ;
REITH, W .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1980, (02) :52-53
[6]   ISOLATION AND SYNTHESIS OF 3-HYDROXY-1 AND 4-HYDROXY-1,7-DIOXASPIRO[5.5]UNDECANES FROM THE OLIVE FLY (DACUS-OLEAE) [J].
BAKER, R ;
HERBERT, RH ;
PARTON, AH .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1982, (11) :601-603
[7]  
BALLINI R, 1992, J CHEM SOC P1, P3151
[8]   Polyketide origin of pheromones of Carpophilus davidsoni and C-mutilatus (Coleoptera: Nitidulidae) [J].
Bartelt, RJ ;
Weisleder, D .
BIOORGANIC & MEDICINAL CHEMISTRY, 1996, 4 (03) :429-438
[9]  
BERGSTROM G, 1982, Z NATURFORSCH C, V37, P1124
[10]   PHEROMONES .53. SYNTHESIS OF (3S,6R)-3-HYDROXY-1,7-DIOXASPIRO [5.5]UNDECANE AND (3S,6S)-3-HYDROXY-1,7-DIOXASPIRO[5.5]UNDECANE - A COMPONENT OF OLIVE FLY PHEROMONE COMPLEX (DACUS-OLEAE) [J].
BESTMANN, HJ ;
SCHMIDT, M .
TETRAHEDRON LETTERS, 1986, 27 (18) :1999-2000