Palladium-Catalyzed β‑C(sp3)−H Nitrooxylation of Ketones and Amides Using Practical Oxidants

Yuan Xue,‡ Han Seul Park,‡ Chao Jiang,* and Jin-Quan Yu*

Herein, we report a Pd(II)-catalyzed β-C(sp3)−H nitrooxylation of ketones and native amides. The fine-tuned removable aminooxyamide auxiliary enabled β-C(sp³)−H functionalization of various aliphatic ketones. Practical iron(III) nitrate nonahydrate was used as the nitrate source and asingle-electron oxidant for Pd(II)/Pd(III)/Pd(IV) catalysis. For amide substrates, N-iodosuccinimide (NIS) was applied as a bystanding two-electron oxidant in combination with silver nitrate for β-C(sp3)−H nitrooxylation. Palladacycle intermediates were isolated and characterized to elucidate the reaction mechanism for the C(sp3)−H activation of ketones with the L,X-type imino-amide directing group.

KEYWORDS: C−H activation, palladium, ketones, amides, nitrooxylation, organic nitrate, palladacycle

https://pubs.acs.org/doi/10.1021/acscatal.1c04188