Triplet Energy Transfer-Mediated Intermolecular Paternò–Büchi Reaction for the Synthesis of Trifluoromethylated Oxetanes
Yining Zhu, Anthony J. Fernandes, Egor Zhilin, Dmitry Katayev
TL;DR
This paper introduces a new light-based method to create trifluoromethylated oxetanes, which are useful in drug development.
Contribution
A novel visible-light-mediated Paternò–Büchi reaction for synthesizing trifluoromethylated oxetanes with high selectivity.
Findings
The method produces a broad range of CF3-containing oxetanes with excellent regio- and diastereoselectivity.
Mechanistic studies show the [2 + 2] cycloaddition proceeds preferentially from the triplet excited state of the CF3-substituted carbonyl partner.
Abstract
Oxetanes are increasingly used as compact, polar carbonyl (bio)isosteres in drug discovery, and the combination with a trifluoromethyl group enables fine-tuning of molecular properties. Here, we report a visible-light-mediated Paternò–Büchi strategy that accesses CF3-containing oxetanes via triplet-energy-transfer activation and delivers a broad range of CF3-containing oxetane products with excellent regio- and diastereoselectivity. Mechanistic studies indicate that although sensitization of both the alkene and carbonyl occurs in solution, the subsequent stepwise [2 + 2] cycloaddition proceeds preferentially from the triplet excited state of the CF3-substituted carbonyl partner.
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Taxonomy
TopicsFluorine in Organic Chemistry · Radical Photochemical Reactions · Synthesis and Catalytic Reactions