ENANTIOSELECTIVE TRIPLET SENSITIZATION REACTIONS

项目摘要/摘要 光化学反应构成了一套不发达的生物医学使能技术 研究。这些反应将对新药和生物探针的发现具有重要价值。 因为光的吸收会导致高能电子激发中间体的形成 这会产生紧张和不寻常的分子结构，而这些分子结构是无法用其他方法合成的。 然而，对这些高能产品的精确三维形状的控制 中间体一直是一个长期存在的挑战，没有通用的解决方案。 这一提议是基于发现了一种以前未知的效应，即路易斯酸配位 作用于有机分子的激发态。我们将研究如何利用这种效应来 控制用光化学反应产生的化合物的三维形状。特别是， 本研究的三个具体目的是探讨这一效应的共性。 目标1.我们正在探索使用这一战略可获得的产品的共性。 目标2.我们正在探索使用这种策略可以激活的有机底物的普遍性。 目的3.我们正在探索催化三联体敏化到其他各种催化平台的共性 激活。 这些方法解决了有机合成中一个重要的百年问题。因此，我们预计 我们的研究成果将对基础学术化学研究和 关于生物医学科学家合成和发现下一代救命药物的能力。

PROJECT SUMMARY/ABSTRACT Photochemical reactions constitute an underdeveloped set of enabling technologies for biomedical research. These reactions would be of great value to the discovery of new drugs and biological probes because the absorption of light results in the formation of high-energy, electronically excited intermediates that can produce strained and unusual molecular architectures that can be synthesized in no other way. However, control over the precise three-dimensional shapes of the products arising from these high-energy intermediates has been a long-standing challenge with no general solutions. This Proposal is based upon the discovery of a previously unknown effect that Lewis acid coordination exerts upon the excited states of organic molecules. We will study how this effect can be exploited to control the three-dimensional shape of compounds produced using photochemical reactions. In particular, the three Specific Aims of this research center on an exploration of the generality of this effect. Aim 1. We are exploring the generality of products that are accessible using this strategy. Aim 2. We are exploring the generality of organic substrates that can be activated using this strategy. Aim 3. We are exploring the generality of catalytic triplet sensitization to various other platforms for catalytic activation. These methods address an important, century-old problem in organic synthesis. Thus, we expect that the results of our research will have significant impacts both in fundamental academic chemical research and on the ability of biomedical scientists to synthesize and discover the next generation of life-saving drugs.