76015-08-2Relevant academic research and scientific papers
Chain-extension Reactions of Acetylenes. Part 4. Reaction of 1,3-Dilithioacetylides with Carbonyl Electrophiles, Hexamethylphosphoric Triamide, and Benzylideneaniline
Pover, Keith A.,Scheinmann, Feodor
, p. 2338 - 2345 (2007/10/02)
The regioselectivity of the reactions of 1,3-dilithioalk-1-ynes with various electrophiles has been examined.With formaldehyde and cyclic ketones, reaction occur at C-1 and C-3 to give alk-2-yne-1,5-diols.In contrast reactions with carbon dioxide give allene-1,3-dicarboxylic acids. 1,3-Dilithioalk-1-ynes decompose hexamethylphosphoric triamide and the resulting N-methylmethyleneamine undergoes addition only at the propargylic site.Further reaction with either 1-bromobutane or water gives alkynylamines.Benzylideneaniline also reacts with 1,3-dilithiohex- and hept-1-ynes only at the propargylic site to give N-phenylbut-3-ynylamines.
