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Reactivity of ynamides with AlCl and ICl: Ready access to (E)-α-chloroenamides and (E/Z)-α-chloro-β-iodo-enamides

Journal of Chemical Sciences, ISSN: 0973-7103, Vol: 133, Issue: 1
2021
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Abstract: AlCl acts as a chlorinating agent for ynamides in the presence of stoichiometric amount of water in the environmentally benign solvent dimethylcarbonate, affording efficient access to (E)-α-chloroenamides via hydrochlorination, with water as a protic source. The role of water in the reaction was proven by deuterium labelling experiment. Epoxy-ynamides undergo iodochlorination in addition to the cleavage of the epoxy ring to afford (E/Z)-α-chloro-β-iodo-enamides. Regio- and stereochemical assignments for the products are based on X-ray crystallographic studies. Graphic abstract: Chloroenamides are formed regio- and stereo-specifically via hydrochlorination of ynamides with AlCl+HO (1:1) in a dimethyl carbonate; aryl substituted epoxy ynamides afford (iodo)(chloro) enamides upon treatment with ICl.[Figure not available: see fulltext.]

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