NATURALLY OCCURRING POLYENES VIA ORGANOMETALLICS

由多个烯烃位点组成的天然化合物在生理活性物质中占有特殊的地位。多烯类包括(1)多烯大环内酯类抗生素，临床上具有抗真菌作用。形成离子通道的材料通常在共轭阵列中包含4到7个e -烯烃。使用连接试剂快速制备具有立体均相形式的氧四到七烯亚段；(2)将研究产生具有轴向手性的联芳基的新途径，特别是万古霉素和米舍拉明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。这两个靶标将通过有机金属中间体获得分子内联芳基偶联策略。立体感应将由连接单个芳基组分的系链的性质来控制。因此，本申请不仅讨论了在当前资助期间取得的可观的已发表进展，还讨论了大量未发表的数据，这些数据支持我们在此概述的多烯项目的继续发展，特别是新的发展方向。在胺和(b)镍炭作为一种有效的，廉价的和环保的催化剂来影响C-C波段的形成，这将有助于我们达到我们的目标，并为合成界提供一般的效用。

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this application discusses not only considerable published progress made during the currant grant period, but extensive unpublished data in support of both the continuing and especially, the new directions in our polyene program, outlined herein.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.