170805-75-1Relevant academic research and scientific papers
Acetylenic Amides. 2. The Generation and Reactions of Dianions Derived From 2-Propynamides
Coppola, Gary M.,Damon, Robert E.
, p. 1133 - 1140 (2007/10/02)
The dianion of N-benzyl-2-propynamide can be generated by the treatment of 4 with two equivalents of LDA at -65 deg C or ethylmagnesium bromide at -20 deg C.The trilithio species 6 is readily formed using 3 equivalents of LDA.Reaction of 5 with aldehydes or ketones produce hydroxypropynamides 9 in good yields.Silation of 5a with chlorotrimethylsilane produces N-benzyl-3-trimethylsilyl-2-propynamide (13) in high yield.Reduction of 9 furnishes either fully saturated amides 15 or partially reduced cis-olefins 16 or 18.Compounds 16, on heating, rearrange to 4-ketoamides 17.Carboxylation of 5a with carbon dioxide produces 3-benzyl-2,4-dioxo-5-oxazidinylacetic acid (11).Warming 11 in dimethyl sulfoxide results in the loss of carbon dioxide and the formation of N-benzylpyruvamide (21).
