Azaxylylenes and Quinomethanes in Photoassisted DOS: Experimental and Theoretical Study

University Of Denver, Denver CO

Investigators

Abstract

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.