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Please login to access the full content or check if you have access via25.1.2.2.4 Variation 4: Oxidation of Alcohols with a Nitroxide and a Co-oxidant
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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.
Me eeeeeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee eeeeeeeeee, eeeee eeeeeeeeee eee eeeeee eeeeeee, ee eeeeeeeee.[888] 8,8,8,8-Meeeeeeeeeeeeeeeeeee-8-eeee ee e eeeeeeeeeeee eeeeeeeee, eeee eeeeeeeee, eee eeee eeeeeee, eeeee eeeeeeeee e eeeee eeeeeee ee eeeeeeeeeeeeeee. Me ee eeeeeee ee eee eeeeeee eeeeeeee eee eeeee ee eeeeee ee eeee ee ee eeeee eeeee. Me eeeeeeeeeee eeeeeee ee eeeeeeeeeeee eee eeeeeeee eeeeee eeeeeeeeee eeee eeeeeee eeeeee eeeeeeeee;[888,888] eeee eeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee e eeeeeeee eeeeeeee eee eee eeeeeeeee ee eeeeeeeeeeeeeeee eeee β-eeeee eeeeeeee.[888,888] Meeee, eee eeee eeeeeee eeeeeeeeeee eeeeeeee eeeeeee eeee eeeeeeeee eeeeeeee eeeeee ee ee eeeeeee eeeee eeeee eee eeeeeeee ee eeeeeeee eeeeeeeee eee eee eeeeeeeee ee eeeeeeee ee eeeeeee; eee eeee eeeeeeeee eeeeeeeeee eee eeeeeeeeeee ee Meeeee 88.[888,888] Meeeee eeeeeeeeeeee (eeeeee) ee eee eeee eeeeeeeeee eeee ee-eeeeeee ee eeeeeeeeeee eeee e eeeeeeeee eeeeee (8.88–8.888 eeeee) ee 8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee. Me ee eeee eeee eeeeeeee eeee 8.88 eeeeeeeeeee ee eeeeee eeeeee eeeeeee[888] ee eeeeeeeee eeeeeee[888,888] ee eeeeeeeee ee e eeeeeeee eeeeeeee (eM 8.8–8.8) ee eeeeeeeeeeeeeee/eeeee. Mee eeeeeeeeee eeeeeeee eeeeeeee ee eeeeeeeee eeeeeee eeeeee eeee eeeeeeeee ee eeee eeee e 8–88 eeee eeeee, eee ee eeeeeeeeeeee eeeeeee eeee 88–88°M eee eeeeeeee eeeeeeeeee. Meeeeeee eeeeeeeeeeeeeeeeee eeeeeee eee M-eeeeeeeeeeeeeeeee eee ee eeee eeeeeeee eeee 8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee ee eeeeeeeeeeee eeeeeee eeeee-8-ee,[88] eeee eeeeee ee eee ee-eeeeeee eee eeeeeeee ee e eeeeeeeee eeeeee ee e eeeeeeeeee eeee eeeee ee eeeeeeeeeeeee eeeeeeee eeeeeeeeee eeeee.[888]
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]
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
[18] | Meeeeee, M.; Meeeeee, M.; Meeeeeeee, M.; Meeeee, M.-M., M. Mee. Meee., (8888) 88, 8888. |
[21] | Meeeeeeeee, M. M.; Meeeee, M. M.; Meeeée, M. M.; Meee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[117] | Meeeeeee, M.; Meeeeeeee, M.; Meeeeeeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 888. |
[118] | Meeeee, M. M. M. M.; Meeeeee, M. M., Me Meeeee Meeeeeeee Meeeeee, Mäeeeeee, M.-M., Me.; Meeee-MMM: Meeeeeee, Meeeeee, (8888); e 88. |
[119] | ee Meee, M. M. M.; Meeeeee, M. M.; eee Meeeee, M., Meeeeeeee, (8888), 8888. |
[120] | Meee, M.; Meeeee, M. M.; Meeeeeeeee, M. M., Mee. Meee., (8888) 8, 8888. |
[121] | Meeeee, M. M.; Meeeeeee, M. M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[122] | Meeeeee, M.; Meeee, M.; Meeeeeeee, M.; Meeee, M.; Meeeeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[123] | Me Meee, M.; Meeeeeeee, M.; Meeeeeee, M.; Meeeeee, M.; Meeeeeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[124] | Meeeeee, M.; Meeeeee, M. M.; Meeee, M.; Meeeee, M., Meeeeee, (8888), 8888. |
[125] | Meeeee, M. M.; Meeee, M. M.; Meeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[126] | Meeáe, M.; Meeeeeeee, M.; Meeeeñe, M., M. Mee. Meee., (8888) 88, 8888. |
[127] | Meee, M.; Meeeeeee, M.; Meeeee, M. M.; Meeeee, M., Mee. M. Mee. Meee., (8888), 888. |
[128] | Meeeee, M. M.; Meeeeeeee, M.; Meeee, M., Mee. Meeee., Meee. Mee. MMMM, (8888), 888. |
[129] | Meeeee, M. M.; Meeee, M.; Meeeeeeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.