SYNTHETIC & MECHANISTIC STUDIES OF URETHANE ENOLATES

本项目的具体目标(由 美国国立卫生研究院拨款A1 19133-06和GM 31256-11，均为三项 年)包括将这些赠款合并为一项 资助期为四年。此外，更重要的是， 我们希望利用技术开发一些全合成技术 我们已经在开发过程中几年了。这个 该方法的中心是使用乙烯基氨基甲酸酯作为四种- 羟醛缩合反应和酰化缩合反应中的碳合成子。 这四个碳合成子通过它们丰富的 功能及其扭曲的几何结构，几个强大的 综合优势，相对于其他烯醇化系统，在这两个 羟醛和酰化反应模式。我们希望能证明 这些优势在几个不同的背景下总计 合成物，每一个都设计成具有这些优点中的一个或另一个 有趣而新奇的感恩节。 最后，我们提出了几种不同的方法来实现更好的 从机械上理解这些孤立的系统是如何工作的。 我们展示了一些非常富有成效的协作工作 Paul Wllliard教授，并提出了进一步的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系统及其衍生物在 这项工作的进程。

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.