Chemical Dynamics and Green Chemistry Strategies with Solid-to-Solid Reactions

有机化学和高分子化学项目继续支持加州大学洛杉矶分校化学系米格尔·A·加西亚-加里巴伊教授的工作。这项研究将研究固态光化学反应和固体到固体反应的绿色化学策略。我们将对几种具有稳定自由基取代基的结晶环己酮衍生物进行一系列的机理研究。这些化合物可以进行干净的脱羰基反应，为制备晶体中的自由基对和双自由基提供了可靠的途径。考虑到前列腺素的合成，将进行旨在解决不饱和羰基化合物的光化学反应的研究。将对影响这些固态光化学反应的量子产率和选择性的因素进行评估。还将进行更多的研究，探索晶体中双自由基和单线态卡宾的化学行为。还将研究量子力学隧道效应在固态反应中的作用。参与这项研究的研究生、本科生和博士后将接受从合成有机化学和固态化学到材料科学的跨学科培训。这一研究项目将继续成功地努力吸引女性和少数族裔学生进入高度支持和创造性的环境。这项工作的影响超越了加州大学洛杉矶分校，通过与几个邻近的没有博士项目的机构进行研究合作。建议的研究结果将有助于解决固体化学和绿色化学中的重要问题。

With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Miguel A. Garcia-Garibay, of the Chemistry Department at the University of California-Los Angeles. This research will investigate solid-state photochemical reactions and green chemistry strategies with solid-to-solid reactions. A series of mechanistic studies with several crystalline cyclohexanone derivatives possessing radical-stabilizing substituents will be carried out. These compounds, which can undergo a clean decarbonylation reaction, will provide a reliable entry to the preparation of radical pairs and biradicals in crystals. With the synthesis of prostaglandins in mind, studies designed to address the photochemical reactivity of unsaturated carbonyl compounds will be undertaken. Factors that affect the quantum yield and selectivity of these solid-state photochemical reactions will be evaluated. Additional studies that probe the chemical behavior of biradicals and singlet carbenes in crystals will be carried out. The role of quantum mechanical tunneling in solid-state reactions will also be investigated.Graduate, undergraduate and post-doctoral students involved in this research will receive interdisciplinary training in techniques and methods that range from synthetic organic and solid-state chemistry to materials science. This research project will continue successful efforts to attract female and minority students to a highly supportive and creative environment. The impact of this work extends beyond UCLA through research collaborations with several neighboring institutions with no Ph.D. programs. The results of the proposed research will contribute to the solution of important problems in solid-state and green chemistry.