Azaxylylenes and Quinomethanes in Photoassisted DOS: Experimental and Theoretical Study

在这个由化学学部化学结构、动力学和机制B项目资助的项目中，丹佛大学的Andrei Kutateladze教授正在开发一种新的光辅助合成复杂杂环的途径。光化学反应未被合成界充分利用，它在构建高强度的碳环和杂环支架方面具有无与伦比的前景，提供了通过基态化学无法获得的困难合成目标的快速途径。该项目旨在填补这一空白，为合成化学家的工具箱开发新的光辅助方法。光化学是一种绿色化学，因为它使用光作为关键试剂。紫外LED辐射器将与高通量合成仪器相结合，以增强现代合成基础设施。该课程为研究生和本科生提供广泛而广泛的培训，结合了苛刻的合成工作，光化学和光物理实验，以及计算机辅助分子建模。该项目侧重于开发一种新的光辅助合成方法，该方法将产生由各种官能团装饰的拓扑多样化的多杂环支架，以及由这些新型核心框架刚性或半刚性地保持在独特空间结构中的碳/杂环吊坠。结构多样的支架是通过关键的光化学步骤实现的，最突出的是通过激发态分子内质子转移产生的偶氮基乙烯和醌的分子内环加成反应。将进行实验和理论机制研究，以评估氮基二甲苯三重态物种的参与。

In this project funded by the Chemical Structure, Dynamics and Mechanisms B program of the Chemistry Division, Professor Andrei Kutateladze of the University of Denver is developing novel photoassisted synthetic pathways to complex heterocycles. Underutilized by the synthetic community, photochemical reactions hold unparalleled promise for building prohibitively strained carbocyclic and heterocyclic scaffolds, offering expeditious access to difficult synthetic targets not accessible via ground state chemistry. This project aims to fill this void, developing new photoassisted methodology for the synthetic chemist's toolbox. Photochemistry constitutes a greener chemistry because it uses light as a key reagent. UV LED irradiators will be combined with high throughput synthetic instrumentation to enhance the modern infrastructure for synthesis. This program provides broad and extensive training for graduate and undergraduate research students, combining demanding synthetic work, photochemical and photophysical experiments, and computer-assisted molecular modeling. The project focuses on the development of a new photoassisted synthetic methodology which will yield topologically diverse polyheterocyclic scaffolds decorated by various functional groups and carbo/heterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these novel core frameworks. Topologically diverse scaffolds are realized via key photochemical steps, most prominently the intramolecular cycloaddition reactions of azaxylylenes and quinomethanes generated via excited state intramolecular proton transfer. An experimental and theoretical mechanistic study will be carried out to assess the involvement of azaxylylene triplet species.