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Tomé, A. C., Science of Synthesis Knowledge Updates, (2015) 2, 81.
The reaction of alkyl, aryl, and sulfonyl azides with lithium, magnesium, sodium, or potassium acetylides is a classic approach to produce 1,5-disubstituted 1,2,3-triazoles regioselectively. The mechanism of these reactions involves a nucleophilic attack of the acetylenic anion on the terminal nitrogen of the azide, followed by 1,5-anionic cyclization to give a triazolyl anion that, after protonation, gives the expected triazole. This methodology can be exemplified by the reaction of lithium acetylides with arylsulfonyl azides to form 5-substituted 1-sulfonyl-1,2,3-triazoles (Scheme 20).[290] Similarly, azides react with chloro- or bromomagnesium acetylides to deliver, regioselectively, 1,5-disubstituted 1,2,3-triazoles. The 4-metallotriazole intermediates can be trapped with different electrophiles to form 1,4,5-trisubstituted 1,2,3-triazoles regioselectively.[291–295]
M eeeeee eeeeeeeeeee eeeeeeee eee eeeeeeeee ee eeeeeeeeeeeeeee 8-eeee-8,8,8-eeeeeeeee 88 ee eeeeeeee eeee eeeeee eeee eeeeee eeeeeeeee eee 88 eeeeeee ee eeee eeeeeeeeeee (Meeeee 88).[888]
Meeeee 88 Meeeeeeeeee ee 8-Meee-8,8,8-eeeeeeeee[888]
Me8 | Meeee (%) | Mee |
---|---|---|
Me | 88 | [888] |
8-Mee | 88 | [888] |
8-Mee | 88 | [888] |
8-Mee | 88 | [888] |
8-MeMM8M8 | 88 | [888] |
8-MeMM8M8 | 88 | [888] |
8-MeM8M8 | 88 | [888] |
8-MeM8M8 | 88 | [888] |
8-MeM8M8 | 88 | [888] |
8-M8MM8M8 | 88 | [888] |
8-M8MM8M8 | 88 | [888] |
8-M8MM8M8 | 88 | [888] |
8-(M8MM8M)M8M8 | 88 | [888] |
Meeeeeeeee ee eeee eeeeee, eeeeeeeee eeeee eeeee eeeeeeeeee (ee eeeee eeeeee), eeee eeee eeeeeeeee ee eeeeee eeeee.[888] Me eeeeeeee, eeee eeeeee ee 8,8-eeeeeeeeeeeee 8,8,8-eeeeeeeee eee eeeeeeee eeee eeeeee-eeeeeeeee eeeeeeeeeeeee ee eeeeeee eeeeee eee eeeeeeee eeeeeeeeee,[888] eeeeee eeeeeeeeee,[888] eee eeee eeeeeeeeee.[888,888] M eeeeeee eeeeeeeee eeeeeeee eee eeeeeeee ee eeee(M) eeeeee eeee eeeeeeee eeeeeee.[888,888] Mee eeeeeeee ee eeeeee(M) eeeeeeeeee eeee eeeeeee eeeeee, ee eee eeeeeeee ee M-eeeeeeeeeeeeeeeee, ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee, eeeeeee 8,8-eeeeeeeeeeeee 8-eeeeee-8,8,8-eeeeeeeee ee 88–88% eeeee.[888] M eee-eee eeeeeeee ee eeeeee(M) eeeeeeeeee, eeeeeee eeeeee, eee eeeee eeeeee eeeeeeee, ee eeeeeeeeeeeee ee eeee eeeeeeeeeee eee 8 eeeee, eeeeeee 8,8,8-eeeeeeeeeeeeee 8,8,8-eeeeeeeee eeeeeee e MMMM8M8 eeeee ee eeeeeeee 8 ee 88–88% eeeee.[888]
Meeeeeeeeeee Meeeeeeee
8-Meee-8,8,8-eeeeeeeee 88; Meeeeee Meeeeeeee:[888]
MMMMMMM: Meee eeeeee eee eeeeeeeee, eee eeeeeeeeeee eeeeeeeee ee eeeeeeee ee eeee, eeeee, eee eeeeeeee.
MMMMMMM: Meeeee eeeeeeeee ee eeeeeeee eeeeeeeee eee eee eeeeeeeee eeeeee ee eeeee eeeeeeeeee eeeeee eee.
MMMM (8 eM) eee eeee eeeee (8.8 eeee) eeee eeeee ee e eeeee-eeeeeeee eeeee. Mee eeeee eee eeeeeeee eeee e eeeeee eeeeee eee eeeeee eeeeeeeee (88 ee% eeeeeeeeee ee eeeeee; 8.8 eeee) eee eeeeeeeeeeee eeeee ee eee eeeeee eee eeeeeee. Meeee eee eeeeeee eee eeee eeeeeee eee 88 eee ee ee, eee eeeeeeee eee eeeeeeee eeee eee eeeeeeee ee M8M (88 eM). Mee eeeeeee eee eeeeeeeee eeee Me8M (8 × 88 eM) eee eee eeeeeeee eeeeeee eeeee eee eeeeee eeee M8M, eee eeeee (MeMM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).
References
[290] | Meee-Meeñe, M. M.; Meeee, M. M.; Mee, M. M.; Meeee, M. M.; Meeeee, M. M., Mee. Meee., (8888) 88, 8888. |
[291] | Meeeeeeee, M.; Meeee, M. M.; Meeeeeeee, M. M., Mee. Meee., (8888) 8, 8888. |
[292] | Mee, M.; Mee, M.; Mee, M.; Meeee, M., Mee. Meee., (8888) 8, 8888. |
[293] | Meeeeeeee, M.; Meeeee, M.; Meeeeeee, M.; Mee, M.; Meee, M.; Meee, M.; Meeeee, M.; Meee, M., Mee. Meeeeee Mee. Mee., (8888) 88, 8888. |
[294] | Mee, M.; Meeeeeeeee, M.; Meee, M.; Meeeeee, M. M.; Meeeeee, M. M., Meeeee. Mee. Meee. Meee., (8888) 88, 888. |
[295] | Meeee, M. M.; Meee, M. M.; Meeeeee, M. M.; Meeeeeee-Meeee, M. M.; Mee, M. M.; Meeee, M. M., Meeeee. Mee. Meee., (8888) 88, 8888. |
[296] | Meeee, M.; Meeee, M.; Meee, M., Meeeeeeeeee, (8888) 88, 888. |
[297] | Meeeeeeeeee, M.; Meeee, M. M.; Meeeee, M. M., Meee.–Mee. M., (8888) 88, 8888. |
[298] | Meee, M.; Meeeeee, M.; Meeeeee, M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[299] | Meeeeeeee, M. M.; Meeeeeeeee, M.; Meeeeeeeee, M. M.; Mee, M. M.; Meeee, M.; Meeeee, M.; Meeeeeee, M. M.; M’Meee, M. M. M.; Meeeeeee, M. M.; Meeeeeee, M. M., Mee. Meeeee. Meee., (8888) 8, 8888. |
[300] | Meeeeee, M. M.; Mee, M.; Meeee, M. M.; Meeeeeeee, M. M., MMM; Meeeeeeee, M.; Meee, M. M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
[301] | Meeeeee, M. M.; Meeeeeeee, M.; Meeeeeeee, M. M.; Meee, M. M., Meee. Meeeee. (Meeeeeeee), (8888) 88, 8888. |
[302] | Meeeeee, M. M.; Meeeeeeee, M. M., MMM; Meeeee, M.; Meeeee, M. M.; Meee, M. M., Meeeeeeeeeeeeee, (8888) 88, 888. |
[303] | Meeeeeeee, M. M.; Meeeeeeee, M.; Meeeeeeee, M. M., MMM; Meee, M. M., Meeee. Meee., (8888) 88, 8888. |
[304] | Meee, M.; Meeee, M.; Meee, M.; Mee, M.; Meee, M.; Me, M., M. Mee. Meee., (8888) 88, 88 888. |
[305] | Meee, M.; Meeee, M. M.; Meeee, M.; Meee, M.; Meee, M.; Me, M., Meeeeeeeeee Meee., (8888) 88, 8888. |