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

Herein, we report a Pd(II)-catalyzed beta-C(sp(3))-H nitrooxylation of ketones and native amides. The fine-tuned removable aminooxyamide auxiliary enabled beta-C(sp(3))-H functionalization of various aliphatic ketones. Practical iron(III) nitrate nonahydrate was used as the nitrate source and a single-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 beta-C(sp(3))-H nitrooxylation. Palladacycle intermediates were isolated and characterized to elucidate the reaction mechanism for the C(sp(3))-H activation of ketones with the L,X-type imino-amide directing group.

Automated summary

In this study, a Pd(II)-catalyzed beta-C(sp(3))-H nitrooxylation of ketones and native amides was reported. The use of fine-tuned removable aminooxyamide auxiliary enabled beta-C(sp(3))-H functionalization of various aliphatic ketones. Palladacycle intermediates were isolated to elucidate the reaction mechanism for ketones C(sp(3))-H activation with the L,X-type imino-amide directing group.