Science of Synthesis

Podlech, J., Science of Synthesis, (2007) 25, 41.

Although other nitroxides have been recommended, mostly as catalytic reagents,[‌117‌] only 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) finds wide application for the oxidation of alcohols ‌25‌ to aldehydes ‌26‌ (see ‌Scheme 19‌).[‌118‌,‌119‌] It may be used in catalytic amounts together with sodium hypochlorite, calcium hypochlorite,[‌117‌] sodium bromite,[‌117‌] Oxone,[‌120‌] N-chlorosuccinimide,[‌18‌] (diacetoxyiodo)benzene,[‌121‌–‌123‌] or copper(II) chloride[‌21‌] as stoichiometric co-oxidants. Reactions in which (diacetoxyiodo)benzene is used can be accelerated by the addition of 1 mol% methanesulfonic acid.[‌121‌] Utilization of oxygen as a co-catalyst for an oxidation with 2,2,6,6-tetramethylpiperidin-1-oxyl is described in Section ‌25.1.2.2.5‌. Unfortunately, care must be taken when using 2,2,6,6-tetramethylpiperidin-1-oxyl as it is a toxic irritant, which is readily absorbed through the skin.

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‌Meeeee 88‌ Meeeeeeee ee Meeeeee Meeeeeee eeee Meeeeeeee 8,8,8,8-Meeeeeeeeeeeeeeeeeee-8-eeee eee e Meeeeeeeeeeeee Me-eeeeeee[‌88‌,‌888‌–‌888‌,‌888‌–‌888‌]

‌Meeeeeeeeee 88‌

M8	Me-eeeeeee	Meeeeeeeee	Meeee(%)	Mee
	MeMMe	MMe (eee.)	88	[‌888‌,‌888‌]
	MeMMe	MeMe, MeMMM8, 8°M, 8 e	88	[‌888‌]
	MeMMe	MeMe, MeMMM8, M8M, eeeeeee, MeMMe, 8°M	88e	[‌888‌]
	MeM(MMe)8	MeMM (8 eee%), MMMe8	88	[‌888‌]
	MeM(MMe)8	MM8Me8, MeMM, ee, 8 e	88	[‌888‌]
(MM8)8Me	MMM	MMMMM, MM8Me8, M8M, ee, 8.8 e	888	[‌88‌]

e 888% ee (eeee 88% ee eee eeeeeeee eeee eee Meeee eeeeee).

Meeeeeeeeeee Meeeeeeee

(M)-8-(Meeeeeeeeeeeeeeeeeeeee)-8-(eeee-eeeeeeeeeeeeeeeeeee)eeeeeeee [‌88‌, M8 = MM(MMMee)MM8MMMMMM]; Meeeeee Meeeeeeee:[‌888‌]

Me MeMMe (8.8 eeee) eee MeMMM8 (8.8 eeee) eeee eeeee eeeeeeee eeee e eeeeee ee 8–8 e ee e eeee (8°M), eeeeeee eeeeeee (>8888 eee) eeeeeeee eeeeeee ee eee M-eeeeee ee eee eeeeeee ‌88‌ [M8 = MM(MMMee)MM8MMMMMM; 8 eeee], MMMMM (8.88 eeee), MeMe (8 eeee), eeeeeee (8 eM), MeMMe (8 eM), eee M8M (8.8 eM). Meeee eee eeeeeeee, eee eeeeeee eeeee eee eeeeeeeee eee eeeeee eeee Me8M (8 eM). Mee eeeeeeee eeeeeeee eeee eeeeee ee eeee eeee MM (8 ee) ee 88% ee MMMM8 (8 eM), 88% ee MeM8M8 (8 eM), eee eeeee (8 eM), eee eeee eeeee (MeMM8). Meeeeeeeee eee eeeeeeeeeeeee eeeee eeeeeee eeeeeeee eeeeeeee eee eeeeeee eeeeeeee, eeeee eee eeee eeeeeeeeeee ee eeeeeee eeeeeeeee; eeeee: 88%.

Meeeeeeee ‌88‌; Meeeeee Meeeeeeee Meeee (Meeeeeeeeeeee)eeeeeee ee Me-eeeeeee:[‌888‌]

MeM(MMe)8 (888 ee, 8.8 eeee) eee eeeee ee e eeee ee ee eeeeeee (8 eeee) eee MMMMM (88 ee, 8.8 eeee) ee MM8Me8 (8 eM). Mee eeeeeee eee eeeeeee eeeee eee eeeeeee eee ee eeeeee eeeeeeeeee (MMM), eee eeee ee eee eeeeeee eeee MM8Me8 (8 eM). Mee eeeeeee eee eeeeee eeee eee. ee Me8M8M8 (8 eM) eee eeeeeeeee eeee MM8Me8 (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee ee MeMMM8 (8 eM) eee eeeee (8 eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeee eeeeeeeeeeeeee ee eeeeeeeeeeeeeee eeeeeeee eeee eeeeeeee.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8/8, 888.
• 8.Meeeee-Meee, (8888) M 8, 888.