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Reactivity of ynamides with AlCl3 and ICl: Ready access to (E)-α-chloroenamides and (E/Z)-α-chloro-β-iodo-enamides

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Abstract

AlCl3 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 AlCl3+H2O (1:1) in a dimethyl carbonate; aryl substituted epoxy ynamides afford (iodo)(chloro) enamides upon treatment with ICl.

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  15. Our earlier work on ynamides: (a) Siva Reddy A, Nagarjuna Reddy M and Kumara Swamy K C 2014 A simple copper-catalysed tandem cyclisation of ynamides leading to triazolo-1,2,4-benzothiadiazine-1,1-dioxides in PEG-400 medium RSC Adv. 4 28359; (b) Siva Reddy A and Kumara Swamy K C 2015 Use of Elemental Sulfur or Selenium in a Novel One-Pot Copper-Catalyzed Tandem Cyclization of Functionalized Ynamides Leading to Benzosultams Org. Lett. 17 2996; (c) Siva Reddy A, Kumari, A L S, Saha S and Kumara Swamy K C 2016 Palladium-Catalyzed Tandem-Cyclization of Functionalized Ynamides: An Approach to Benzosultams Adv. Synth. Catal. 358 1625; (d) Kumari A L S, Siva Reddy A and Kumara Swamy K C 2016 Transition Metal-Free Cascade Cyclization of Epoxy-Ynamides: To Go for 1,3-Oxazines or 1,4-Oxazines? Org. Lett. 18 5752; (e) Anitha M, Shankar M and Kumara Swamy K C 2019 Reactivity of epoxy-ynamides with metal halides: nucleophile (Br/Cl/OH)-assisted tandem intramolecular 5-exo-dig or 6-endo-dig cyclisation and AgF2-promoted oxidation Org. Chem. Front. 6 1133; (f) Siva Reddy A and Kumara Swamy K C 2017 Ethanol as a Hydrogenating Agent: Palladium-Catalyzed Stereoselective Hydrogenation of Ynamides To Give Enamides Angew. Chem. Int. Ed. 56 6984

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  18. For another recent example, see: Anitha M and Kumara Swamy K C 2019 Highly functionalised (γ-azido/γ-fluoro-β-iodo/) vinyl derivatives from phosphorus based allenes or allenoates: I···O halogen bonding interactions Org. Biomol. Chem. 17 5736

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Acknowledgements

We thank the Department of Science and Technology (DST, New Delhi) and University Grants Commission (UGC, New Delhi) for support. ASR, MA and Suraj thank UGC (New Delhi) for fellowships. KCK thanks SERB for the J. C. Bose fellowship.

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  1. School of Chemistry, University of Hyderabad, Hyderabad, 500 046, Telangana, India

    Alla Siva Reddy, Mandala Anitha,  Suraj & K C Kumara Swamy

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  1. Alla Siva Reddy
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  2. Mandala Anitha
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Correspondence to K C Kumara Swamy.

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Siva Reddy, A., Anitha, M., Suraj et al. Reactivity of ynamides with AlCl3 and ICl: Ready access to (E)-α-chloroenamides and (E/Z)-α-chloro-β-iodo-enamides. J Chem Sci 133, 6 (2021). https://doi.org/10.1007/s12039-020-01880-4

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