Visible-Light-Promoted Metal-Free Ammoxidation of C(sp3)-H bonds

24 August 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The metal-free activation of C(sp3)-H bonds to value-added products is of paramount importance in organic synthesis. Herein, we report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photo process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as L-menthol, amino acids and cholesterol derivatives. Further, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments and NMR‑ spectroscopic as well as kinetic studies, all supporting the proposed catalytic cycle.

Keywords

Photoredox catalysis
nitriles RCN
C-H functionalization
methylarenes
Ammoxidation

Supplementary materials

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Title
PC Ammoxidation ChemRxiv SI
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