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Tandem transformations of bromo-substituted β-(methylsulfonyl)styrenes in reactions with dimethyl malonate, methyl cyanoacetate, and methyl acetoacetate

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Abstract

β-Bromo-β-(methylsulfonyl)styrene reacted with dimethyl malonate and methyl cyanoacetate in the presence of sodium hydride to give sulfonyl-substituted cyclopropanes, and sulfonyl-substituted 2,3-dihydrofuran was also formed in the reaction with methyl acetoacetate. Reactions of α-bromo-β-(bromomethylsulfonyl) styrene with dimethyl malonate and methyl cyanoacetate led to the formation of 2,3-dihydro-λ6-thiophene S,S-dioxide derivatives. In the reaction of α-bromo-β-(bromomethylsulfonyl)styrene with methyl acetoacetate, 2,3-dihydro-λ6-thiophene S,S-dioxide and 2,5-dihydro-λ6-thiophene S,S-dioxide derivatives and methyl acetoacetate O-alkylation product, methyl 3-[(E)-2-(bromomethylsulfonyl)-1-phenylvinyloxy]but-2-enoate, were obtained at a ratio of 2.7: 1.2: 1. α-Bromo-β-(methylsulfonyl)styrene reacted with dimethyl malonate to produce dimethyl 2-[2-(methylsulfonyl)-1-phenylethylidene]malonate. The reaction of β-bromo-β-(bromomethylsulfonyl) styrene with dimethyl malonate and methyl cyanoacetate were strictly stereoselective, and they afforded tetrahydro-λ6-thiophene S,S-dioxide derivatives. The reaction of the same substituted styrene with methyl acetoacetate was not stereoselective, and the products were two diastereoisomeric tetrahydro-λ6-thiophene S,S-dioxides and sulfonyl-substituted 2,3-dihydrofuran at a ratio of 2.3: 2.7: 1.

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Authors and Affiliations

  1. Ogarev Mordoviya State University, ul. Bol’shevistskaya 68, Saransk, 430005, Russia

    V. A. Vasin & I. Yu. Bolusheva

  2. St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504, Russia

    V. V. Razin

  3. Lobachevskii State University of Nizhni Novgorod, pr. Gagarina 23, Nizhni Novgorod, 603950, Russia

    N. V. Somov

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  1. V. A. Vasin
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  2. I. Yu. Bolusheva
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  3. V. V. Razin
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  4. N. V. Somov
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Correspondence to V. A. Vasin.

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Original Russian Text © V.A. Vasin, I.Yu. Bolusheva, V.V. Razin, N.V. Somov, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 7, pp. 1011–1020.

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Vasin, V.A., Bolusheva, I.Y., Razin, V.V. et al. Tandem transformations of bromo-substituted β-(methylsulfonyl)styrenes in reactions with dimethyl malonate, methyl cyanoacetate, and methyl acetoacetate. Russ J Org Chem 50, 993–1002 (2014). https://doi.org/10.1134/S1070428014070100

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  • DOI: https://doi.org/10.1134/S1070428014070100

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