SYNTHETIC & MECHANISTIC STUDIES OF URETHANE ENOLATES

该项目的具体目标（由 美国国立卫生研究院根据赠款A1 19133-06和GM 31256-11，都是三个 （a）将这些赠款合并为一项 为期四年的补助金。 此外，更重要的是， 我们希望开发一些全合成技术， 我们已经发展了好几年。 的 该方法的中心是使用插烯聚氨酯作为四元聚氨酯， 在羟醛缩合和酰化缩合中均存在碳负离子。 这四个碳分子凭借其丰富的 功能和它们扭曲的几何形状，几个强大的 相对于其他烯醇化物系统， 羟醛缩合和酰化反应模式。 我们希望展示 这些优点在几个不同的总体范围内， 综合，每个设计的特点一个或另一个优点，这些 有趣和新颖的烯醇化物。 最后，我们提出了几种不同的方法，以更好地 这些烯醇化物系统如何工作的机械理解。 我们展示了一些非常富有成效的合作工作， Paul Wllliard教授，并提出进一步的X射线实验， 回答有趣和令人兴奋的新问题， 提出了关于这些烯醇化物系统及其衍生物， 这项工作的过程。

The specific aims of this project (which have been sponsored by the NIH under grants A1 19133-06 and GM 31256-11, both three years each) include the consolidation of these grants into one grant of four year duration. In addition, and more importantly, we wish to develop a number of total syntheses using technology we have been in the process of developing for several years. The method centers around the use of vinylogous urethanes as four- carbon-synthons in both the aldol and acylation condensations. These four carbon synthons provide, by virtue of their rich functionality and their twisted geometries, several powerful synthetic advantages, relative to other enolate systems, in both the aldol and acylation reaction modes. We hope to demonstrate these advantages within the context of several different total syntheses, each designed to feature one or another virtue of these interesting and novel enolates. Lastly, we propose several different approaches towards a better mechanistic understanding of how these enolate systems work. We demonstrate some very fruitful collaborative work with Professor Paul Wllliard, and propose further X-ray experiments to answer interesting and exciting new questions that have been raised about these enolate systems and their derivatives during the course of this work.