Synlett 2018; 29(05): 571-575
DOI: 10.1055/s-0036-1589151
letter
© Georg Thieme Verlag Stuttgart · New York

Facile Synthesis of β-Keto Sulfones Employing Fenton’s Reagent in DMSO

Petrakis N. Chalikidi
a  K. L. Khetagurov North Ossetian State University, Vatutina St. 46, 362025 Vladikavkaz, Russian Federation   Email: hampazero@mail.ru
,
Maxim G. Uchuskin
b  Perm State University, Bukireva 15, 614990 Perm, Russian Federation
,
Igor V. Trushkov
c  Faculty of Science, RUDN University, Miklukho-Maklaya 6, 117198 Moscow, Russian Federation
,
Vladimir T. Abaev*
a  K. L. Khetagurov North Ossetian State University, Vatutina St. 46, 362025 Vladikavkaz, Russian Federation   Email: hampazero@mail.ru
,
Olga V. Serdyuk*
d  Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Henkestrasse 42, 91054 Erlangen, Germany   Email: oserduke@mail.ru
› Author Affiliations
The authors thank the Russian Foundation for Basic Research (Grant No. 16-03-00807) for financial support.
Further Information

Publication History

Received: 26 October 2017

Accepted after revision: 16 November 2017

Publication Date:
02 January 2018 (online)

Dedicated to the memory of Professor Alexander V. Butin, colleague and close friend

Abstract

A new facile method for the synthesis of β-keto sulfones employing xanthates, DMSO, and Fenton’s reagent is described. The reaction proceeds under very mild conditions providing a cost-effective straightforward approach to various β-keto sulfones in high yields.

Supporting Information

 
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  • 22 Representative Experimental Procedure for the Synthesis of Compound 3a 34% H2O2 (2 mL, 20 mmol) was added to a cooled solution of FeSO4·7Н2О (2.78 g, 10 mmol) in DMSO (40 mL), and the mixture was stirred for 30 min at 5–10 °C. Then, xanthate 1a (2.4 g, 10 mmol), FeSO4·7Н2О (2.78 g, 10 mmol), and H2O2(2 mL, 20 mmol) were added and the reaction mixture was stirred for 30 min at 5–10 °C and, then, 2 h at r.t. (TLC control). The reaction mixture was poured into H2O (30 mL) and extracted with EtOAc (4 × 50 mL). The combined organic phases were washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure. The resulting crude mixture of products was purified by silica column chromatography using EtOAc–PE (1:4) as eluents. The yield of compound 3a was 1.71 g (86%). Characterization Data of Representative Compounds 3
    2-(Methylsulfonyl)-1-phenylethanone (3a) 23
    Pale yellow solid (1.71 g, isolated yield 86%); mp 107–109 °C (PE–EtOAc = 2:1), lit. 86–90 °C.23 1H NMR (400 MHz, DMSO-d 6): δ = 8.10–7.97 (m, 2 H), 7.72 (m, 1 H), 7.58 (dd, J = 10.7, 4.9 Hz, 2 H), 5.11 (s, 2 H), 3.16 (s, 3 H) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 190.59, 136.34, 134.75, 129.50, 129.31, 61.23, 42.51 ppm. ESI-HRMS: m/z calcd for C9H10O3SNa [M + Na]+: 221.0248; found: 221.0242. Ethyl 2-(Methylsulfonyl)acetate (3l)24 Colorless oil (1.295 g, isolated yield 78%). 1H NMR (400 MHz, CDCl3): δ = 4.25 (q, J = 7.1 Hz, 2 H), 3.99 (s, 2 H), 3.12 (s, 3 H), 1.29 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 163.10, 62.65, 59.12, 41.62, 13.95 ppm. ESI-HRMS: m/z calcd for C5H10O3SNa [M + Na]+: 189.0197; found: 189.0189.
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