Latcruculins是在细胞生物学中用于阻断肌动蛋白聚合的海洋毒素。因此,开发新的合成策略和合成方法对于提高合成策略和方法非常重要,调节或控制这种生物学价值。文献中发现的全部合成都针对类似的断开连接,特别是涉及复发性4-乙酰基-1,3-噻唑烷-2-酮伴侣的羟醛策略。在这里,我们描述了另一种断开和随后的立体选择性转换,以构建适合于latrunculin和类似物合成的立体定向。从(+)-β-香茅烯开始。关键的立体选择性转化涉及不对称的Krische烯丙基化,在1,5-反立体控制下的羟醛反应,和Tishchenko-Evans减少伴随着特殊的酯置换,允许安装天然产品的关键立体中心。
Latrunculins are marine toxins used in cell biology to block actin polymerization. The development of new synthetic strategies and methods for their synthesis is thus important in order to improve, modulate or control this biological value. The total syntheses found in the literature all target similar disconnections, especially an aldol strategy involving a recurrent 4-acetyl-1,3-thiazolidin-2-one ketone partner. Herein, we describe an alternative disconnection and subsequent stereoselective transformations to construct a stereopentade amenable to latrunculin and analogue synthesis, starting from (+)-β-citronellene. Key stereoselective transformations involve an asymmetric Krische allylation, an aldol reaction under 1,5-anti stereocontrol, and a Tishchenko-Evans reduction accompanied by a peculiar ester transposition, allowing to install key stereogenic centers of the natural products.