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性质， 和具有以下通用结构的二烯基醚-铁配合物： CpFe（CO）2（p12-omicronl）BF 4。 在这个项目中，我们建议建立 合成异构二烯基类的一般方法， 聚烯基醚-铁络合物，并举例说明它们在合成中的用途， 乙烯基阳离子阴离子和作为反极性组分[2+4] 环加成反应 发现了一种简单的方法 高光学纯度的光学活性乙烯基醚-铁络合物， 定义的绝对配置为第二部分提供了背景 的提案。 我们的目标是研究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， β-羟基醛和酸的绝对控制 在α和β不对称中心都具有构型。 一种有效 免疫抑制剂的必需氨基酸成分的合成 基于这种化学反应， 此外该 这些旋光试剂在不对称[2+4]环加成中的用途 反应和Claisen重排将被检查。 其化学性质是本研究主题的络合物将构成 一类新的具有独特化学反应性的质子， 亲和力逆转和对映体分化是必需的， 独特的功能。 它们应提供宝贵的新方法， 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.