These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
ZhengDong-rxiv.pdf (2.02 MB)

Divergent Photocatalytic Reactions of α-Ketoesters Under Triplet Sensitization and Photoredox Conditions

submitted on 04.07.2020, 21:03 and posted on 06.07.2020, 11:52 by Jian Zheng, Xiao Dong, Tehshik Yoon
The long-lived triplet excited states of transition metal photocatalysts can activate organic substrates via either energy- or electron-transfer pathways, and the rates of these processes can be influenced by rational tuning of the reaction conditions. The characteristic reactive intermediates that are generated by each of these activation modalities, however, are distinct and can exhibit very different reactivity patterns. Herein, we show that the photocatalytic reactions of benzoylformate esters with alkenes can be directed towards either Paternò–Büchi cycloadditions under conditions that favor energy transfer or allylic functionalization reactions under superficially similar conditions that favor electron transfer. These studies provide a framework for designing other divergent photocatalytic methods that produce different sets of reaction outcomes under photoredox and triplet sensitization conditions.


NIH GM095666


Email Address of Submitting Author


University of Wisconsin-Madison, Department of Chemistry


United States

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest

Usage metrics