Stereochemical Control of Photo-reactions within Zeolites

本研究项目以发展基于沸石/手性催化剂组合的不对称光化学反应为目标。这是基于沸石中可以包括不止一个分子或类型的客体分子的事实。在没有现成的手性沸石的情况下，通过在沸石中加入手性有机分子来创造一个不对称的环境。将研究的光反应包括二烯的Zimmerman(二皮甲烷)重排，酮的Norrish-Yang(第二类)反应，β-伽马不饱和烯酮的氧杂-二皮甲烷重排，以及聚烯的电环化。拉马穆尔蒂教授研究的是光激活化学反应，这种化学反应发生在某些天然和人造矿物分子尺度的孔洞内，这些矿物被称为沸石。通过允许某种分子与反应物分子一起进入沸石空腔，可以更好地控制反应过程中的进行。通过这种方式，可以获得制药业使用的高附加值物质。此外，我们对分子与沸石相互作用的方式以及这种相互作用如何影响随后的光化学的理解将得到加强。

This research project has as its goal the development of asymmetric photochemical reactions based on a zeolite / chiral catalyst combination. This is based on the fact that more than one molecule or type of guest molecule can be included within a zeolite. In the absence of readily available chiral zeolites, an asymmetric environment will be created by including chiral organic molecules within zeolites. Photoreactions to be studied include the Zimmerman (di-pi-methane) rearrangement of dienes, the Norrish-Yang (Type II) reaction of ketones, oxa-di-pi-methane rearrangement of beta-gamma-unsaturated enones, and electrocyclization of polyenes.With this Award, the Organic and Macromolecular Chemistry Program supports the research of Professor Vaidyanathan Ramamurthy of Tulane University. Professor Ramamurthy studies light-activated chemical reactions that take place inside the molecular scale pores of certain natural and man-made minerals called zeolites. By permitting a certain kind of molecule to enter the zeolite cavity along with the reactant molecule, it may be possible to gain better control over the goings-on during the reaction. In this way, high value-added substances of use for the pharmaceutical industry might be accessed. Further, our understanding of the way in which molecules interact with zeolites and how this interaction affects the subsequent photochemistry will be enhanced.