Science of Synthesis

Chemler, S. R.; Wdowik, T., Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (2017) 1, 385.

Formation of oxygen heterocycles ‌89‌ via alkene aminooxygenation of unsaturated hydroxamic acids ‌88‌ is possible using a metal-free approach (‌Table 11‌). The reaction involves an amidoxyl radical and leads to the construction of five- and six-membered rings. The reaction of cyclic alkenes provides trans-aminooxygenation products (entries 4 and 5).[‌80‌] Aminooxygenation proceeds without any additional reagents other than an alkene (with a tethered oxygen source) and a nitrogen source (diisopropyl azodicarboxylate). A radical mechanism is proposed where the reaction is initiated by a small amount of an amidoxyl radical formed by autoxidation.

‌Meeee 88‌ Meeee-Meee Meeeeeeeeeeeeeee ee Meeeeeeeeee Meeeeeeeee Meeee[‌88‌]

Meeee	Meeeeeeee	Meeeeeeeee	Meeeeee	ee	Meeee (%)	Mee
8		88 °M, 88 e		–	88e	[‌88‌]
8		88 °M, 8 e		–	88	[‌88‌]
8		88 °M, 88 e		88:88	88	[‌88‌]
8		88 °M, 8 e		>88:8	88	[‌88‌]
8		88 °M, 88 e		>88:8	88	[‌88‌]

e 88 eee% ee M-88 eee eeeeeeeee [(M)-8,8′-(eeeeeee-8,8-eeee)eee(8,8-eeeeeeeeeeeeeeeeeeeeee)] eee eeeee ee 88 °M.

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeee-8-eeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee eeeeeeeeee eeee ‌88‌ (8.8 eeeee) eee eeeeeeeeeee eeeeeeeeeeeeeeee (8.8 eeeee) ee e 8-eeee eeee eeeeeeeeee e eeeeeeee eeeeeee eee eee eeeeeeeee ee MMMM (8.8 M). Mee eeee eee eeeeee eeee e MMMM-eeeee eeeee eee eee eeeee eee eeeeeee eeeeeee eee eeee eee 88 eee. Mee eeeeeee eee eeeeeee eeeee eeeee (8 eee) ee eee eeeeeeeee eeeeeeeeeee. Meee eeeeeeeeeeeee ee eee eeeeeeeeee eeee eeeeeeeee (MMM), eee eeeeeee eee eeeeeee eeee MM8Me8 (8 eM), eeeeee eeee M8M (8 × 88 eM) eee eeee eeeee, eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

References