Direct Iodosulfonylation of Alkylynones with Sulfonylhydrazides and Iodine Pentoxide Leading to Multisubstituted α,β-Enones

§ These authors contributed equally to this work

Abstract

A facile and efficient method has been developed for the construction of multisubstituted α,β-enones through the direct selective iodosulfonylation of alkylynones with sulfonylhydrazides and iodine pentoxide. The present methodology offers a simple and attractive approach to various multisubstituted α,β-enones in moderate to good yields with excellent stereo- and regioselectivities under the metal- and peroxide-free conditions.

Key words

multifunctionalized α,β-enones - iodosulfonylation - alkylynones - sulfonylhydrazides - iodine pentoxide

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• 15 Preparation of (E)-3-iodo-1,3-diphenyl-2-(phenylsulfonyl)prop-2-en-1-one (4aa): In a 25 mL round-bottomed flack, alkylynone 1a (0.125 mmol), sulfonylhydrazide 2a (0.375 mmol), I₂O₅ (3; 0.125 mmol), and DME (2 mL) were added. The reaction mixture was stirred at 80 °C for 12 h. After completion the reaction, the solvent was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired product 4aa. Yield: 49 mg (83%). ¹H NMR (CDCl₃, 400 MHz): δ = 8.28 (d, J = 7.2 Hz, 2 H), 7.72 (t, J = 7.3 Hz, 1 H), 7.62 (t, J = 7.8 Hz, 2 H), 7.54 (t, J = 7.4 Hz, 1 H), 7.49 (d, J = 7.3 Hz, 2 H), 7.36–7.26 (m, 5 H), 7.17 (d, J = 6.6 Hz, 2 H); ¹³C NMR (CDCl₃, 100 MHz): δ = 190.6, 149.3, 140.4, 140.0, 134.7, 133.8, 133.7, 130.3, 129.6, 129.3, 129.0, 128.8, 128.3, 128.0, 127.5; HRMS: m/z [M + Na]⁺ calcd. for C₂₁H₁₅IO₃SNa: 496.9684; found: 496.9689.