VINYL ETHER-IRON COMPLEXES--NEW ORGANIC SYNTHONS

这项研究计划的目的是研究乙烯基的化学 和一般结构的二烯基醚-铁配合物： CPFE(CO)2(Pi2-omicronl)BF4.在这项计划中，我们建议建立 双烯基异构体和异构体的一般合成方法 多烯基醚-铁络合物及其在合成中的应用 反极性的乙烯基阳离子合成子和As组分[2+4] 环加成反应。发现了一种简单的准备方法 光学活性的乙烯基醚-铁配合物，光学纯度高， 定义的绝对配置为第二部分提供了背景 这项提议。我们的目标是检查这些系统的使用情况 为了实现高效和高度灵活的不对称合成 完全控制绝对控制的β-羟基醛和酸 α和β不对称中心的构型。一种高效的 免疫抑制剂必需氨基酸成分的合成 药物环孢素是基于这种化学作用而设计的。此外， 这些光学活性试剂在不对称[2+4]环加成反应中的应用 将考察反应和克莱森重排。 其化学为本研究主题的络合物将构成 一类新的具有独特化学反应活性的合成子，其中电荷 亲和力逆转和对映面分化是必不可少的 独特的功能。它们应该提供有价值的新方法 合成化学家。

The objective of this research proposal is to study the chemistry of vinyl and dienyl ether-iron complexes of general structure: CpFe(CO)2(pi2-omicronl)BF4. Within this program, we propose to establish general methods for the synthesis of classes of isomeric dienyl and polyenyl ether-iron complexes and to illustrate their use in synthesis as vinyl cation synthons and as components in reverse polarity [2+4] cyclo-addition reactions. The discovery of a simple means of preparing optically active vinyl ether-iron complexes of high optical purity and defined absolute configuration provides the background for the second part of the proposal. Our objective here is to examine the use of these systems for effecting efficient and highly flexible asymmetric syntheses of beta-hydroxyaldehydes and acids with complete control of absolute configuration at both the alpha and beta asymmetric centers. An efficient synthesis of the essential amino acid constituent of the immunosuppressive drug cyclosporin is projected, based on this chemistry. In addition, the use of these optically active reagents in assymmetric [2+4] cycloaddition reactions and Claisen rearrangements will be examined. The complexes whose chemistry is the subject of this study will constitute a new class of synthons of unique chemical reactivity in which charge affinity reversal and enantiofacial differentiation are essential and unique features. They should provide valuable new methodology for the synthetic chemist.