Azaxylylenes and Quinomethanes in Photoassisted DOS: Experimental and Theoretical Study

光辅助 DOS 中的氮二甲苯和喹诺甲烷：实验和理论研究

• 批准号: 1362959
• 负责人: Andrei Kutateladze
• 金额: $ 30万
• 依托单位: University of Denver
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362959&HistoricalAwards=false
• 关键词: Azaxylylenes; Quinomethanes; Photoassisted; DOS; Experimental

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.

在这个由化学系化学结构，动力学和机制B计划资助的项目中，丹佛大学的Andrei Kutateladze教授正在开发复杂杂环的新型光辅助合成途径。 未被合成界充分利用的光化学反应为构建过度紧张的碳环和杂环支架提供了无与伦比的希望，为通过基态化学无法获得的困难合成目标提供了快速的途径。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。 UV LED辐照器将与高通量合成仪器相结合，以增强现代化的合成基础设施。 该计划为研究生和本科生研究生提供广泛而广泛的培训，结合了要求苛刻的合成工作，光化学和光物理实验以及计算机辅助分子建模。该项目的重点是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和碳/杂环悬垂物装饰的拓扑多样的多杂环支架，这些新型核心框架刚性或半刚性地保持在独特的空间构型中。拓扑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氮杂亚甲基和醌甲烷的分子内环加成反应。 将进行实验和理论机理研究，以评估氮杂亚甲基三重态物种的参与。