Total synthesis of himachalene sesquiterpenes of Aphthona and Phyllotreta flea beetles

被引：27

作者：

Bartelt, RJ ^{[1
]}

Weisleder, D ^{[1
]}

Momany, FA ^{[1
]}

机构：

[1] USDA ARS, Natl Ctr Agr Utilizat Res, Peoria, IL 61604 USA

来源：

SYNTHESIS-STUTTGART | 2003年 / 01期

关键词：

himachalene; terpenoids; pheromones; annulations; stereoselective synthesis; natural products;

D O I：

10.1055/s-2003-36253

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A total synthesis is presented for himachalene-related norsesquiterpene ketone 1 (racemic), based on the Robinson annulation and other standard reactions. The route involved five steps from cycloheptanone. A favorable result was that the desired diastereomer of 1 was obtained preferentially (97:3) over the unwanted one. Molecular modeling (ab initio calculations) aided in confirming the assignment of relative stereochemistry of 1 and in rationalizing the observed ratio of diastereomers. Three related sesquiterpene hydrocarbons and two alcohols were subsequently produced from 1. The six compounds occur naturally in several flea beetle species and likely serve a pheromonal function.

引用

页码：117 / 123

页数：7

共 17 条

[1] Male-specific sesquiterpenes from Phyllotreta and Aphthona flea beetles [J].

Bartelt, RJ ;

Cossé, AA ;

Zilkowski, BW ;

Weisleder, D ;

Momany, FA .

JOURNAL OF CHEMICAL ECOLOGY, 2001, 27 (12) :2397-2423

[2]

Boeckman Jr R., 1978, ORG SYNTH, V58, P158

[3]

Boeckman R. K., 1978, ORG SYNTH, V58, P152

[4] REACTION OF LITHIUM ALKYLS WITH ALDEHYDES AND KETONES - GENERAL STUDY [J].

BUHLER, JD .

JOURNAL OF ORGANIC CHEMISTRY, 1973, 38 (05) :904-906

[5] A 2ND GENERATION FORCE-FIELD FOR THE SIMULATION OF PROTEINS, NUCLEIC-ACIDS, AND ORGANIC-MOLECULES [J].

CORNELL, WD ;

CIEPLAK, P ;

BAYLY, CI ;

GOULD, IR ;

MERZ, KM ;

FERGUSON, DM ;

SPELLMEYER, DC ;

FOX, T ;

CALDWELL, JW ;

KOLLMAN, PA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (19) :5179-5197

[6] THE RELATIONSHIP BETWEEN PROTON-PROTON NMR COUPLING-CONSTANTS AND SUBSTITUENT ELECTRONEGATIVITIES .1. AN EMPIRICAL GENERALIZATION OF THE KARPLUS EQUATION [J].

HAASNOOT, CAG ;

DELEEUW, FAAM ;

ALTONA, C .

TETRAHEDRON, 1980, 36 (19) :2783-2792

[7]

House H.O., 1965, MODERN SYNTHETIC REA

[8] N-BUTYLTHIOMETHYLENE BLOCKING GROUP [J].

IRELAND, RE ;

MARSHALL, JA .

JOURNAL OF ORGANIC CHEMISTRY, 1962, 27 (05) :1615-&

[9]

JOLY R, 1958, B SOC CHIM FR, P367

[10]

KHAN VA, 1989, CHEM NAT COMPD, P606

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