Science of Synthesis

Jonczyk, A.; Kowalkowska, A., Science of Synthesis, (2006) 8, 1031.

Reactions of carbanions, generated from methine CH acids, with alkynes leads to the formation of their vinylated products. In the case of methylene CH acids, more complex processes take place. Phase-transfer-catalyzed addition of 2-phenylalkanenitriles to acetylene and its derivatives is usually carried out in dimethyl sulfoxide in the presence of powdered potassium hydroxide and benzyltriethylammonium chloride as a catalyst,[‌279‌] but sodium hydroxide is occasionally used for this purpose. The powdered sodium hydroxide–dimethyl sulfoxide–Q+X− system is used for vinylation of 2-substituted N-(benzylidene)glycinonitriles with acetylene, phenyl- and ethoxyacetylene,[‌280‌] or 2-(N-morpholino)phenylacetonitrile with acetylene.[‌281‌] Reaction of arylacetonitriles ‌34‌, substituted at C2 with different amino groups, with acetylene furnishes substituted 1,3-dienamines.[‌281‌] Carbanions from these CH acids undergo addition to phenyl-, (methylsulfanyl)-, and methoxyacetylenes[‌282‌] or 1-phenyl- or 1-(methylsulfanyl)prop-1-yne[‌283‌] resulting in the formation of the corresponding vinylated compounds ‌35‌ and/or the products ‌36‌ of the reaction of 2 equivalents of the alkyne with 1 equivalent of the nitrile (‌Scheme 31‌). The ratio of these two kinds of products depends upon the basicity of the amine, i.e. the concentration of the ammonium salts which are in equilibrium with the aminonitriles, but the conditions also affect the reaction outcome.[‌282‌,‌283‌]

‌Meeeee 88‌ Meeeeeeee ee 8-(Meeeeeeeeeee)eeeeeeeeeeeeeeeee eeee Meeeeeeeeeeeeee Meeeeeeeee[‌888‌]

Meeeee- eee eeeeeeeeeeeeeeeee eeeeeee eeeeeeeeeeeee eeeeeeeeee eee eeeeeee ee eeeeeee eeee eeeeee ee eee eee eee ee eeeeeeeeee ee eeeeeeeee ee eeeeeeeee eeee eeeeeee eeeee.[‌888‌] Meeeeeeeeee, eeee ee eeeee eeeeeeeeeee eeeeeee eee ee eeeeeeeee eeeee eeeee-eeeeeeee eeeeeeeee eeeeeeeeee eeee eeee eeeeeeeeee eee eee eeeeeee eeeeeeee ee eeee eeee eeeeeeeeee.[‌888‌] Meee, eee eeeeeeee ee 8-eeeeeeeeeee eeeeeeeeeeeeeeeeeee eeee 8,8-eeeeeeeeeeeeee [ee (M)-8,8-eeeeeeeeeeeeee] ee eee eeeeeeee ee eeeeeeeeeeee eeeeeee eeeeee eeeeeeeee, eeee eeeeeeeeeeeeeeeeee eeeeeeee eeeeeee ee eee eeeeeeee ee e eeeeeee eeeee/eeeeeeeeeee eeeeeee, eeeee ee eee eeeeeeeee ee eeeeeeeeeeeeee ee eeee eeeee. Mee eeeeeeee eeeee eeeee eee e eeeee eeeeeeee ee eee eeeeeee eeeeeeeeee ee eee ee eeee eeeeeeeee eeeeeeeeeeeeeee, eeeeee eeeeeeeee eee M-eeeeeeeeeee eeeeeeeeeee, eeeeeeee ee eeeeeeeeeee ee eeeeeeee eeeeeeee.[‌888‌] Me e eeeeeee eeeeeee, eeeee eeeeeeee eeee eeeeee- ee (eeeeeeeeeeeeee)eeeeeee eeeeeeeeeee eee eee 8,8-eeeeeeee-8-eeeeee- ee 8,8-eeeeeeee-8-(eeeeeeeeeeeeee)eeeeee eeeeeeeeeeeee.[‌888‌] Meeeeeeeeeeeeeeee ee eeeeeeeeeeee eeeeeeeee eeee eeeeeeeeeeeeeee ee eeeee ee 88% eeeeeee eeeeee eeeeeeeee eee eeeeeeeeeeeeeeeeeeeeee eeeeeeee[‌888‌] ee eeeeeeee eeeeeeeee.[‌888‌] Meee eeeeeee ee eeeee ee eeee eeee eee eeeeee eeeeeeeee eeee 8-eeeeeeeeeeeeeeeeeeee[‌888‌] eee α-eeeeeeeeeee eeeeee eeeeeee ‌88‌ ee eeeeeeeeeeeeeeeeeee,[‌888‌] ee eeeee ee eee eeeeeeeee ee eeeeeeeeeeeee eeeeeeee ‌88‌ (‌Meeeee 88‌). Meeeeeee eeee eeeeeeeee eeeeee M-eeeeeeeeeee eeeeeeee, eee eeeeeee eeeeee.[‌888‌] Meeeee eeeeeeeee eeee M-eeeeeeeeeeeeee eeeee eeeee-eeeeeeee eeeeeeeee eeeeeeeeee eeeeeee eeeeeeee eeee eeeeeeeeeeeeeee (eee eeeeeeeeeeeeeeeee) ee eeee eeeeeeee ee eeeeeeeeee eee eeeeeee-8,8-eeeeeeeeeeeeeeeee ee eeee eeeee eeeee.[‌888‌]

‌Meeeee 88‌ Meeee-Meeeeeee-Meeeeeeee Meeeeeeeeeeeeeeeee ee Meeeeeee eee Meeeeee eeee Meeeeeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeeeee Meeeeeeee

(M)-8,8-Meeeeeee-8-eeeeeee-8-eeeeeeeee-8-eeeeeeeeee (‌88‌, M8 = MMe; M8 = MM); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee eeeeeee ee eeeeeee(eeeeee)eeeeeeeeeeee (8.88 e, 88 eeee), 88% ee MeMM (8.8 eM), eee Me8MMMM8 (8.8 e, 8.8 eeee) eee eeeeee ee 8–88°M. Meee, e eeee ee 8,8,8-eeeeeeeeeeeeeee (8.88 e, 88 eeee) ee Me8M (8.8 eM) eee eeeee ee 8–88°M eeee 88 eee. Mee eeeeeee eee eeeeeee ee 8–88°M eee 8 e, eeeeeeeee eeeeeee eeee M8M (88 eM), eee eee eeeeee eeee eeeeeeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee eeeeeee (8 × 88 eM) (MMMMMMM: eeeeeeeeee), eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M (8 × 88 eM), eee eeeee (MeMM8), eee eeeeeeeeee ee eeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeee; eeeee: 8.88 e (88%); ee 888°M/8.8 Meee.

References

Meeeeee Meeeeeeeeee

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