A suite of novel allenes from Australian melolonthine scarab beetles.: Structure, synthesis, and stereochemistry

被引:27
作者
McGrath, MJ
Fletcher, MT
König, WA
Moore, CJ
Cribb, BW
Allsopp, PG
Kitching, W [1 ]
机构
[1] Univ Queensland, Dept Chem, Brisbane, Qld 4072, Australia
[2] Univ Queensland, Dept Zool & Entomol, Brisbane, Qld 4072, Australia
[3] Univ Hamburg, Inst Organ Chem, D-2000 Hamburg, Germany
[4] Dept Primary Ind, Yeerongpilly, Qld, Australia
[5] Bur Sugar Expt Stn, Bundaberg, Qld, Australia
关键词
D O I
10.1021/jo026213j
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A suite of allenic hydrocarbons, previously unknown as a molecular class from insects, has been characterized from several Australian melolonthine scarab beetles. The allenes are represented by the formula CH3(CH2)nCH=.=CH(CH2)(7)CH3 with n being 11-15, 17 and 19, and thus, all have Delta(9,10)-unsaturation. These structures have been confirmed by syntheses and comparisons of spectral and chromatographic properties with those of the natural components. The enantiomers of (+/-)-Delta(9,10)-tricosadiene and Delta(9,10)-pentacosadiene were separable on a modified beta-cyclodextrin column (gas chromatography), and the natural Delta(9,10)-tricosadiene (n = 11) and Delta(9,10)-pentacosadiene (n = 13) were shown to be of >85% ee. Syntheses of nonracemic allenes of known predominating chirality were acquired using both organotin chemistry and sulfonylhydrazine intermediates, and comparisons then demonstrated that the natural allenes were predominantly (R)-configured.
引用
收藏
页码:3739 / 3748
页数:10
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