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26.1.1.4.1 Method 1: From Nitroalkanes (The Nef Reaction)

DOI: 10.1055/sos-SD-026-00003

von Angerer, S.Science of Synthesis, (200526113.

Secondary nitroalkanes, which are easily obtained from primary nitroalkanes by base-catalyzed reactions with electrophiles can be converted into ketones, e.g. 168, by various methods, which comprise oxidation, reduction, and treatment with base.[‌444‌] The application of these procedures in organic synthesis has been reviewed.[‌9‌] Potassium permanganate is the most widely used oxidant for this purpose.[‌445‌,‌446‌] A variety of methyl 4-nitroalkanoates have been converted into the corresponding 4-oxoalkanoates by treating the respective nitronate with potassium permanganate (Table 11, entry 1).[‌447‌] In a modification of this reaction potassium permanganate on silica gel is used as the oxidant for the conversion of γ-nitroketones into 1,4-diketones (Table 11, entry 2).[‌448‌]

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8,8-Meeeeeeeeeee[8.8.8]eeeee-8-eee eeeeeee eee eeeeeeeeeeeee ee eeeeeeeeeeee ee eeeeeee. Meee eeeeeeeeee eee ee eeeeeeeeee ee ee eeeeeeee eeeee eeeeeee eeeeeeeee eee eeeeeeeeeeeeeeeee eeeeee eeee eee eee eeeeeeee ee eee eeeee eeeee (Meeee 88, eeeee 88).[‌888‌] 8,8-Meeeeeeeeeee[8.8.8]eeeee-8-eee eeeeeee eee eeeeeeeeeeeeeee ee eee eeeee eeeeeeee ee eee eeeeeeee eeee eeeee eeeeeeeeee eeeeeeeeeee eeee eee eeeeeeeeeee eee eeeeeeeeeeeeee eeeeeeeeeeeee eeee eeeeeeeeeee eeeeeeeee ee eee eeeeee. Meee eee eeeee ee eeeee ­eeeeeeee eeeee ee eeeeeee eeee eeeeeee eeeeeeeeeeee eeee, eeeeeee eee eeeeee eeeee eeeeeeee ee eeeee eeeeee eee M=M eeee eee eeeeeeeeee eeeeeeeeee (Meeee 88, eeeee 88).[‌888‌] M eeee, eeeeeeeee eeeeee eee eeeeeeeeee eeeeeeeee eeeee eeeeeeeee ee eeeeeee eeeeeee eeeeee eeeeeee eee eeeeeeeeeeeee (Meeee 88, eeeee 88).[‌888‌] Mee eeeeeeeeeeeee eeeeeee eee eeeeeeee ee eeee eeeee. Mee eeee ee eeeeeeeee eeeeeeee eeeeeee eee eee eeeeeeeeeeeeee ee eeeee eeeeeeeee ee eeeeeee ee eeeeeeeeeeee ee ee eeeeeeeeeeeeeee eeeeeeeee. Meeeeeeeeeee ee eeeeeeee eeeeeeeeee eeeeeeeeeee eeeeeeee eee eeeee eeeeeeee eeee eeeeeee eeeeeee eeeeeeeee eeeee eee eeeeee eeeeee (Meeee 88, eeeee 88).[‌888‌,‌888‌]

Meeee 88 Meeeeeeeeee ee Meeeeee ee eee Mee Meeeeeee[‌888‌‌888‌]

Meeee Meeeee 888 Meeeeee ee ­Meeeeee Meeeeeeeee Meeee (%) Mee
8 eeeeee 8-eee­eeeeeeeee MMeM8 8. MeMM/MeMMe, 8°M
8. Me8M8M8, M8M, ee
8. MMeM8, M8M, ee
88 [‌888‌]
8 eeeeee-8,8-eeeeee MMeM8 eeeeee eee, eeeeeee, eeeeee, 8e 88 [‌888‌]
8 eeeeee 8-eee-8-eeeeeeeeeeeeeeee Me8MMeM8 ee, 88eee 88 [‌888‌]
8 8-eeeeeeeeeeeeeeeeeeee MeMeM8 Me8MMMM8 (88eee%), MM8Me8, 8M MeMM, ee, 8e 88 [‌888‌]
8 8-eeeeeeeeeee eeee 88% M8M8 MeMM, M8MM8, ee, 88e 88 [‌888‌]
8 8,8-eeeeeeee­eeeee-8,8-eeeeee 88% M8M8 MeMM, M8MM8, 88°M, 88e 88 [‌888‌]
8 eeeeeeeeeeeee MMM MeMM, Me8M, M8M, 88°M, 8e 88 [‌888‌]
8 8-eeeeeeeeeeeeeeee MMMMe MMM, e-MeMM (8.8 eeeee), M8M (8 eeeee) 88 [‌888‌]
8 8-eeeeeeeeeeeeee-8-eee MeMe88M8M MMM, ee, 8e 88 [‌888‌]
88 8-eeeeeeeeeeeeee-8-eee MeMe8 eeeee, ee MM8MMe, MeMMe (8 eeeee), MeMM, ee, 8e 88 [‌888‌]
88 8-eeeeeeeeeeeeeeeeeeee MMM MeMM, 88°M, 8e 88 [‌888‌]
88 8,8-eeeeeeeeeeeee-8,8-eeeee MMe MeMM, ee MeMM, ee, 8.8e; 8M MMe, ee, 8e 88 [‌888‌]
88 eeeeeeeeeeeeee MeMM8, MeMMM M8, MMMM, 8888°M, 8e 88 [‌888‌]
88 eeeeeeee-8,8-eeeeee eeeeeeeeeeee MeMM, MMM8Me, Me eeeeeeeeee, 88 eM, ~8M, 8888°M, 8e (8 M·eee8) 88 [‌888‌]

e Mee eeeeeeeee eee 8-eeeeeeeeee-8-eee.

e Mee eeeeeeeee eee 8,8-eeeeeeee-8-eeeeeeeeee-8-eee.

e MMMM=Meeeeeeeeeeeeeeee (8.8 eeeee, ee eeeeeee).

e Mee eeeeeeeee eee 8-(8-eeeeeeeeee)eeeeeeeeeeeee.

e Mee eeeeeeeee eee 8-eeeeeeeeeeee-8-eee.

Meeee eeee eee eeeeeeeeee ee eeeeeeeee eeeee eeeeeeeee, ee eee Meeeeee eeeeeeee ee eeeeeee eeeee eeeeeeeee ee eeeee eeeeeee eee α,β-eeeeeeeeeee eeeeeeeeee eeeeee, eee eee eeeeeeeeee ee eeeeeeeeeeee eeee eeeeeee eee ee eeeeeeeee eeeee eeee eeeeeeeee, e eee-eee eeeeeeeee eee ee eeeeeee eee eeee eeeeeeee eeeee. 8,8-Meeeeeeeeeee[8.8.8]eeeee-8-eee eee eeee eeeee ee ee eee eeeeeeeeeee eeee eee eeeee eeeeeeeee.[‌888‌,‌888‌] Me eeeeeeeeeee eeeeeeeee eeee eeeeeeeee eeeeeeeee[‌888‌] ee eeeeeee[‌888‌] ee eee eeee eee eee eeeee eeee ee eee eeeeeeee eee eeee eeeeeeee eeeeeeee eee eee eeeeeeeee eeeeeeee ee eee MM eeee. M eeeeeee eeeeeee ee eeee eee-eeee eeeeeeee ee eee eeeeeeeee ee eeeeeee-8,8-eeeee (888, M8=Me) eee eeeeee-8,8-eeeee (888, M8=Me), eeeeeeeeeeee (Meeeee 888).[‌888‌]

Meeeee 888 Mee-Mee Meeeeeeee ee 8,8-Meeeeeeee eeee Meeeeeeeeeee eee Meeee Meeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeee 8-Mee-8-eeeeeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee eeeeee 8-eeeee-8-eeeeeeeeeeeeeeee (88.8ee, 8.888eeee) eee Me8MMeM8 (88.8ee, 8.888eeee) ee MM8Me8 (8eM) eee eeeeeee ee eeeeeee eeeeeeeeeee eee 88eee eeeee eeeee ee eee eeeeeee eeee Me8M eee eeeeeeee eeeeeee Meeeee. Meeeeeeeeeeee ee eee eeeeeeee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M 8:8) eeeeeeee eee eeeeeee ee ee eee; eeeee 88.8ee (88%).

Meeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

Me e eeee-eeeeeee eeeeeee ee eeeeeeeeeeeeeeee (8.88e, 8eeee) eee Me8M (8eM) ee MeMM (88eM) ee e 88-eM eeeee-eeeeeeee eeeee eeeeee eeee e eeeee eeeeeeeee eee eeeee ee ee eeee ee MMM (8.88e, 8eeee) ee M8M (8eM). Mee eeee eeeeee eeee e eeee eeeee eeeeeeee, eeeee eee eeee eeeeee ee 88°M eee eeeeeeeeee ee eeee eeeeeeeeeee eee 8e. Meeee eeeeeeeeee ee eee eeeeeeee, eee eeeeeee eee eeeeee, eeeeeee eeee MeMM (88eM), eee eeeeeeee ee eeeeee eee eeeeeeeee eeeeeeeee. Mee eeeeeeee eee eeeee ee ee Me8M (8×88eM) eee eeeeee eeeeeeeeeeee eeee M8M, eee MMe, eee eeeee. Mee eeeee eeeeeeee eeee eeeeeeeeeeee ee eeee eee eeeeeee; eeeee: 8.88e (88%).

8,8-Meeeeeeee 888 eeee Meeeeee Meeeeeeeeeee; Meeeeee Meeeeeeee:[‌888‌]

M eeee ee eee eeeeeee eeeeeeeeeee (8.8eeee) eee M8MM8 (8eeee) ee M8M (8eM) eee eeeeeee ee ee eee 8eee, eee eeee eee eeeee eeeeee (8.8eeee) eee eeeee. Meeee eee eeeeeee eee eeee eeeeeee ee ee eee 8e, e 88% ee eeee ee M8M8 (8eM) eee eeeee eee eee eeeeeee eee eeeeeee eeeeeeeee ee ee. Mee eeeeeee eee eeee eeeeeeeee eeee MeMMe, eee eeeeeee eeeee eee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee/MeMMe 8:8); eeeee: 8888%.

References