College of Sciences, Northwest A&F University Yangling 712100, Shaanxi, China.
Molecules. 2013 May 7;18(5):5201-8. doi: 10.3390/molecules18055201.
An asymmetric synthesis of 14-methyl-1-octadecene, the sex pheromone of the peach leafminer moth has been achieved. The target molecule was synthesized in six linear steps and in 30.3% overall yield from commercially available hexanoyl chloride, (S)-4-benzyloxazolidin-2-one and 1,9-nonanediol. The hexanoyl chloride was connected with (S)-4-benzyloxazolidin-2-one, and with the induction of the chiral oxazolidinone auxiliary, after chiral methylation, LAH reduction and then tosylation gave the chiral key intermediate 5 in high stereoselectivity. 1,9-Nonanediol, was selectively brominated, THP protected and subjected to Li₂CuCl₄-mediated C-C coupling to afford a C12 intermediate. The target molecule, (S)-14-methyl-1-octadecene, was obtained after the two parts were subjected to a second Li₂CuCl₄-mediated C-C coupling. Our synthetic approach represents the first time a substrate-control asymmetric synthesis of (S)-14-methyl-1-octadecene has been reported.
已经实现了 14-甲基-1-十八烯的不对称合成，14-甲基-1-十八烯是桃潜叶蛾的性信息素。目标分子通过 6 步线性反应，以 30.3%的总收率，从商业可得的己酰氯、(S)-4-苯甲氧基恶唑烷-2-酮和 1,9-壬二醇合成。己酰氯与(S)-4-苯甲氧基恶唑烷-2-酮连接，在手性恶唑烷酮助剂的诱导下，经过手性甲基化、LAH 还原和对甲苯磺酰化，得到高立体选择性的手性关键中间体 5。1,9-壬二醇选择性溴化，THP 保护，然后进行 Li₂CuCl₄介导的 C-C 偶联，得到 C12 中间体。将两个部分进行第二次 Li₂CuCl₄介导的 C-C 偶联后，得到目标分子(S)-14-甲基-1-十八烯。我们的合成方法代表了首次报道的(S)-14-甲基-1-十八烯的底物控制不对称合成。
