Synthesis of E-Aryl Ethenesulfonamides:  A Simple One-Pot, Two-Step Procedure from 1-Hydroxy-1-arylalkanes

Abstract

The unusual reactivity of 1-phenyl-1-ethanesulfonic acid in thionyl chloride was investigated. Mechanistic considerations led us to set up a new and efficient synthesis of E-arylethenesulfonamides starting from 1-hydroxy-1-arylalkanes. The easy availability of the starting materials and the straightforward, one-pot procedure make this process an attractive method for the preparation of these compounds currently largely employed in chemical and pharmaceutical fields.

Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts

“…Another group of syntheses proceeds through transition‐metal‐catalysed allylic substitution–isomerization sequences, or cross‐coupling reactions, using sodium aryl sulfinates or sulfinate surrogates as nucleophiles. In a third class of syntheses, the C–C double bond of the vinylsulfonyl derivatives is formed by elimination of water or hydrogen halide after introduction of the sulfone . An approach to vinylsulfones from terminal alkynes proceeds through hydrozirconation and trapping of the vinylzirconium intermediate with a sulfonyl chloride .…”

Palladium Catalyzed Monoselective α-Arylation of Sulfones and Sulfonamides with 2,2,6,6-Tetramethylpiperidine·ZnCl·LiCl Base and Aryl Bromides

“…The desired product (52.1 mg, 0.19 mmol) was obtained after chromatography (silica gel, heptane/ ethyl acetate gradient) in 38% yield as a colorless solid. 1 H NMR (400 MHz, CDCl 3 ) δ = 2.34 (s,3 H),4.28 (s,2 H),7.18 (t,J = 8.39 Hz,4 H),2 H),2 H),9.91 (s,1 H) ppm; 13 C{1H}NMR (100 MHz, CDCl 3 ) δ = 21.6, 62.7, 128.5, 129.7, 131.5, 134.7, 134.8, 136.2, 145.1, 191.6 Hz,1 H),2 H),7.25 (t,J = 1.76 Hz,1 H),2 H) ppm; 13 C{1H}NMR (100 MHz, CDCl 3 ) δ = 21.6,53.3,111.5,112.7,128.5,129.6,134.8,142.7,143.3 ppm;MS (EI): m/z (%) = 236 [M] + (5), 190 (1), 172 (25), 147 (10), 128 (10), 101 (15), 81 (100); IR: υ = 2922 (w), 1594 (w), 1381 (w), 1308 (s), 1274 (s), 1235 (m), 1148 (s), 1124 (s), 1017 (s), 871 (s), 805 (s) cm −1 . The obtained data match those reported in the literature.…”

“…9 We observed decomposition of substrate 1 upon activation with thionyl chloride followed by an oxidative rearrangement. 10 The corresponding unsaturated side product 3 was obtained exclusively (Scheme 2). 9 In addition, free α-branched benzyl sulfonic acids are sensitive and gradually decompose upon storage.…”

“…In particular, the synthesis of α-branched heterocyclic benzyl sulfonamides proved to be challenging, as the corresponding sulfonyl chlorides readily decompose into the corresponding benzyl chlorides with extrusion of sulfur dioxide (Scheme ). We observed decomposition of substrate 1 upon activation with thionyl chloride followed by an oxidative rearrangement . The corresponding unsaturated side product 3 was obtained exclusively (Scheme ).…”

Reaction of natural-occurring phenolic derivatives with bis(trimethylsilyl) sulfate

“…They were characterized by 1 H NMR, melting point, and as S-benzylthiouronium salts and /or sulfonamide (data not shown). Sulfonamides are widely used in the pharmaceutical industry [6].…”