Gram-Scale Synthesis of β-Sulfonyl Styrenes

Abstract

A simple and gram-scale synthesis of β-sulfonyl styrenes has been developed starting from one-pot PPA (polyphosphoric acid)-catalyzed 1,1-diacetoxylation of arylacetaldehydes (ArCH2CHO) with acetic anhydride (Ac2O) followed by deacetoxylative sulfonylation of the resulting 1,1-diacetate intermediate with sodium sulfinates (RSO2Na) in good yields under solvent-free conditions.

One-pot synthesis of sulfonyl dibenzosuberdiones via In(OTf)3-promoted double Friedel–Crafts reactions of oxygenated arylacetic acids with β-arylvinyl sulfones

“…The other starting β-arylvinyl sulfones 5a-5w (i.e., β-sulfonyl styrenes) were prepared from the one-pot PPA ( polyphosphoric acid)-catalyzed 1,1-diacetoxylation of arylacetaldehydes with acetic anhydride followed by deacetoxylative sulfonylation of the resulting 1,1-diacetate with sodium sulfinates (RSO 2 Na) in good yields under easy-to operate conditions based on previous experience. 8 The initial study commenced with metal triflate 10 -promoted reaction of homoveratric acid 4a (Ar = 3,4-(MeO) 2 C 6 H 3 , 1.0 mmol) and β-arylvinyl sulfones 5a (R = Tol, Ar 1 = Ph, 1.0 mmol). Initially, by using In(OTf ) 3 7a (20 mol%) as the Lewis acid, 11 6a was obtained in 84% yield along with two molecules of water as the byproduct under MeNO 2 (5 mL), 25 °C and 20 h conditions (Table 1, entry 1).…”

“…, β-sulfonyl styrenes) were prepared from the one-pot PPA (polyphosphoric acid)-catalyzed 1,1-diacetoxylation of arylacetaldehydes with acetic anhydride followed by deacetoxylative sulfonylation of the resulting 1,1-diacetate with sodium sulfinates (RSO 2 Na) in good yields under easy-to operate conditions based on previous experience. 8…”

“…In view of this shortcoming, we hoped to develop a one-pot, facile and easy-to-operate synthetic route for obtaining diverse oxygenated dibenzo-fused seven-membered ring skeletons. On the basis of the above-mentioned idea, the expected goal, and the previous research experiences on the synthetic applications of two starting materials arylacetic acids 4 7 and vinyl sulfones 5 , 8 novel sulfonyl dibenzosuberdiones 6 were chosen as the target molecule. To the best of our knowledge, the tricyclic core skeleton of sulfonyl dibenzosuberdiones 6 has not been reported thus far.…”

CuBr2-Mediated One-Pot Synthesis of Sulfonyl 9-Fluorenylidenes

“…Continuing our research on the synthetic applications of β-sulfonyl styrenes, we present a one-pot three-step method for sulfonyl 9-fluorenylidenes 8 via metal halide (MX n )-mediated α-halogenation of o -arylacetophenones 2 (derived from the cross-coupling of o -bromoacetophenones 3 with arylboronic acids 4 ), sodium sulfinates (RSO 2 Na) 6 -mediated substitution of the formed α-bromo o -arylacetophenones 5 , followed by intramolecular Friedel–Crafts-type dehydrative annulation of the resulting α-sulfonyl biarylketones 7 (Scheme ).…”

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds

“…Later, the same group reported a solvent-free sequential one-pot for the synthesis of β-sulfonyl styrenes through a polyphosphoric acid (PPA)-catalyzed 1,1-diacetoxylation of arylacetaldehydes with Ac 2 O, followed by deacetoxylative sulfonylation with sodium sulfinates under solvent-free conditions ( Scheme 83 ). 139 A series of vinyl sulfones was obtained on the gram-scale (5 mmol), and the yields ranged from good to high using different arylacetaldehydes and several aryl and alkyl sulfinates. Aryl vinyl sulfones, benzyl vinyl sulfones, and divinyl sulfones were obtained in acceptable yields.…”