Rapid and Direct Photocatalytic C(sp3)−H Acylation and Arylation in Flow. Issue 39 (20th August 2021)

• Record Type: Journal Article
• Authors: Mazzarella, Daniele; Pulcinella, Antonio; Bovy, Loïc; Broersma, Rémy; Noël, Timothy
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 39(2021)
• Page Start: 21277
• Page End: 21282
• Publication Date: 2021-08-20
• Subjects: acylation -- arylation -- flow chemistry -- hydrogen atom transfer -- TBADT; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202108987
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Herein, we report a photocatalytic procedure that enables the acylation/arylation of unfunctionalized alkyl derivatives in flow. The method exploits the ability of the decatungstate anion to act as a hydrogen atom abstractor and produce nucleophilic carbon‐centered radicals that are intercepted by a nickel catalyst to ultimately forge C(sp 3 )−C(sp 2 ) bonds. Owing to the intensified conditions in flow, the reaction time can be reduced from 12–48 hours to only 5–15 minutes. Finally, kinetic measurements highlight how the intensified conditions do not change the reaction mechanism but reliably speed up the overall process. Abstract : Need for speed: An efficient and fast photocatalytic procedure that enables the acylation/arylation of unfunctionalized alkyl derivatives in flow has been realized by combining decatungstate photocatalysis and nickel catalysis. The methodology shows great functional group tolerance and high regioselectivity, and can be used for the late‐stage functionalization of various biologically‐relevant molecules.