Direct Oxidation of Csp3 -H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow

Mathieu Lesieur; Claudio Battilocchio; Ricardo Labes; Jérôme Jacq; Christophe Genicot; Steven V Ley; Patrick Pasau

doi:10.1002/chem.201805657

Direct Oxidation of Csp³ -H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow

Chemistry. 2019 Jan 24;25(5):1203-1207. doi: 10.1002/chem.201805657. Epub 2018 Dec 14.

Authors

Mathieu Lesieur¹, Claudio Battilocchio^{2

3}, Ricardo Labes², Jérôme Jacq¹, Christophe Genicot¹, Steven V Ley², Patrick Pasau¹

Affiliations

¹ UCB Biopharma, Avenue de l'industrie, 1420, Braine l'Alleud, Belgium.
² Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
³ Syngenta Crop Protection AG, Schaffhauserstrasse, CH-4332, Stein, Switzerland.

PMID: 30485562
DOI: 10.1002/chem.201805657

Abstract

A fast, scalable, and safer C_sp ³ -H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp³ -H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8-99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane.

Keywords: Oxone; TFDO; dioxirane; flow; hydroxylation; oxidation.

Grants and funding

DG06 (convention n°7240)/Service Public de Wallonie