NATURALLY OCCURRING POLYENES VIA ORGANOMETALLICS

由多个烯基组成的天然化合物在生理活性物质中占有特殊的地位。该多烯类化合物包括(1)多烯大环内酯类抗生素，临床上被认为是抗真菌药物。离子通道形成材料通常在共轭阵列中含有四到七个E-烯烃。将寻求使用结合剂快速制备立体化学均一形式的氧代四至庚烯亚段；(2)将研究合成具有轴手性的联芳基的新途径，特别是万古霉素和米歇拉明B的联芳基部分。前者是世界上抵御某些细菌感染的最后一道防线之一，后者是一种特别有效的抗艾滋病化合物。这两个目标都将通过有机金属中间体来自分子内的联芳基偶联策略。立体诱导将由连接单个芳基组分的系绳的性质控制。因此，本申请不仅讨论了在Currant授权期内取得的相当大的已公布进展，而且还讨论了大量未公布的数据，以支持我们在此概述的多烯计划中的持续和特别是新的方向。作为一种有效的、廉价的、对环境无害的催化剂，它可用于形成C-C带，这应有助于我们实现我们的目标，并为合成界提供普遍用途。

Naturally occurring compounds consisting of multiple olefinic sites occupy a special niche among physiologically active agents. Included in this polyene group are (1) the polyene macrolide antibiotics, clinically valued as anti-fungals. The ion channel-forming materials usually contain between four and seven E-olefins in a conjugated array. The use of conjunctive reagents for rapidly preparing oxo tetra- to heptaene subsections in stereochemically homogeneous form is to be pursued; (2) new routes to biaryls bearing axial chirality, in particular the biaryl portions of vancomycin and michellamine B, will be studied. The former is one of the world's last lines of defense against certain bacterial infections, and the latter is an especially effective anti-AIDS compound. Both targets will derive from an intra-molecular biaryl coupling strategy via organometallic intermediates. Stereoinduction will be controlled by the nature of the tether joining the individual aryl components. Thus, this application discusses not only considerable published progress made during the currant grant period, but extensive unpublished data in support of both the continuing and especially, the new directions in our polyene program, outlined herein. In amines, and (b) nickel-on-charcoal as an effective, inexpensive and environmentally benign catalyst for effecting C-C band formations which should assist us in reaching our goals, and provide general utility as well to the synthetic community.