Lithium aminoacetylides

Ficini and Barbara [14, 15] prepared lithium aminoacetylides and allowed them to react with alkyl bromides or tosylates in hexamethylphosphoramide to give good yields of substituted ynamines (Eq. 16). This method shows promise of being a general route to ynamine derivatives. 

Such substitutions using lithium amides, secondary and in some cases tertiary amines as nucleophiles, have been introduced in early sixties as the first expedient method for this unique class of compounds. It is relevant that / ,/ -difluoro- and chlorofluorole-fins readily available through modified Wittig reaction from aldehydes constitute also good ynamine precursors. In the past decade, however, the more versatile lithium aminoacetylide method has gained more prominence. Substitution reactions are still used, among others, for phenyl, tert.-butyl, cinnamyl and cyclopropyl ynamines. 

Hexatriynides can be prepared from lithium aminoacetylides by reaction with perchlorobutenyne. 8 ... 

Lithium 1-aminoacetylides LiC=CNR2 give alkoxy aminocyclopropen-ylidene chromium complexes,34 though in low yield. 

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See also in sourсe #XX -- [ ]

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