Chow Sharon, Fletcher Mary T, Lambert Lynette K, Gallagher Oliver P, Moore Christopher J, Cribb Bronwen W, Allsopp Peter G, Kitching William
Department of Chemistry, School of Molecular and Microbial Science, The University of Queensland, St. Lucia 4072, Australia.
J Org Chem. 2005 Mar 4;70(5):1808-27. doi: 10.1021/jo0481093.
The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus are 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes, 1 and 2, respectively. Stereoisomers of 2,4,6,8-tetramethylundecanal of established relative stereochemistry were derived from 2,4,6-trimethylphenol and were then coupled with appropriate methyl-substituted phosphoranes 62 and 25 to furnish alkenes, which on reduction provided diastereomers of 1 and 2, respectively. Capillary gas chromatography, mass spectrometry, and high resolution 13C NMR spectroscopy confirmed 1 as either 84a or 84b and 2 as either 15a or 15b. The novelty of these structures and their relative stereochemistry is briefly related to polyketide assembly.
甘蔗象甲物种小反颚茧蜂的主要表皮碳氢化合物分别是4,6,8,10,16 - 五甲基和4,6,8,10,16,18 - 六甲基二十二烷，即1和2。具有确定相对立体化学结构的2,4,6,8 - 四甲基十一醛的立体异构体由2,4,6 - 三甲基苯酚衍生而来，然后与适当的甲基取代的磷叶立德62和25偶联以提供烯烃，烯烃经还原分别得到1和2的非对映异构体。毛细管气相色谱法、质谱法和高分辨率13C核磁共振光谱法确定1为84a或84b，2为15a或15b。这些结构及其相对立体化学的新颖性与聚酮化合物组装有简要关联。
