STUDIES ON THE RETINOIDS AND VINYLALLENE CHEMISTRY

类维生素A除了在视觉过程中发挥关键作用外， 以及紫膜（质子泵）的功能。 盐生盐杆菌（Halobacterium halobium），最近已被证明是潜在有用的 作为癌症和皮肤病如痤疮的化疗剂。 该提案的核心涉及结构和 几何异构的丙二烯类视黄酸及其重排， 通过[l，j]-sigmatropic氢位移或其他类型的维甲酸类似物 烯丙基重排 重排后的合成靶标包括 空间位阻几何异构体以及构象锁定， 双键移位或甲基取代的类维生素A。 可能的 维生素A乙酸酯的Diels-Alder加合物向受阻 还将研究视黄醛的几何异构体。 作为合成目标 结构和生物物理性质以及视蛋白结合 各种类似物的能力将被检查作为一种手段， 了解视紫红质，bathorhodopsin和其他物种的结构 与视觉周期有关。 最后，根据初步结果， 关于某些二烯-联烯的电环化的新研究将 接受检查。 为了确定这一方法的范围，德里曼 提出了通过这种新方法从β-紫罗兰酮获得的衍生物， 前体（正/负）-widrol和光学活性warburganal。

Retinoids (vitamin A), besides playing pivotal roles in the visual process as well as in the function of the purple membrane (the proton pump of Halobacterium halobium), has recently been shown to be potentially useful as chemotherapeutic agents in cancer and in skin disorders such as acne. The heart of the proposal concerns the synthesis of structurally and geometrically isomeric allenic retinoids and their rearrangement to retinoid analgoues via [l,j]-sigmatropic hydrogen shifts or other kinds of allylic rearrangements. The synthetic targets after rearrangement include sterically hindered geometric isomers as well as conformationally locked, double bond shifted or methyl substituted retinoids. The possible conversion of the Diels-Alder adduct of vitamin A acetate to hindered geometric isomers of retinal will also be investigated. As synthetic goals are achieved, structural and photophysical properties and the opsin binding ability of the various analogues will be examined as a means of understanding the structure of rhodopsin, bathorhodopsin and other species associated with the visual cycle. Finally, based on preliminary results, new studies regarding the electrocyclization of certain diene-allenes will be examined. In order to establish the scope of this methodology, drimane derivatives obtained from Beta-ionone by this novel method are proposed as precursors to (plus/minus)-widrol and optically active warburganal.