tert-Butyl Hydroperoxide Mediated Cascade Synthesis of 3-Arylsulfonylquinolines

Abstract

3-Arylsulfonylquinoline derivatives play important roles as pharmaceutical drugs. A new method for the synthesis of 3-arylsulfonylquinoline derivatives has been achieved through tert-butyl hydroperoxide mediated cycloaddition between N-propargyl aromatic amine derivatives and arylsulfonylhydrazides without the addition of any metals. This transformation offers a straightforward route to the formation of a C-S bond and quinoline ring in one step via a sulfonylation-cyclization-aromatization process.

Copper(i)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: an electrochemical mechanistic study

“…The latter method was applied for the synthesis of structures containing the b-hydroxysulfone moiety predominantly at a tertiary carbon atom, which cannot be further oxidized (Scheme 1, eqn (2)). 16 For the sulfonylation of unsaturated compounds without additional insertion of oxygen into the molecule, a number of oxidants have been exploited: Cu(OAc) 2 , 17,18 CAN, 19 NBS, 20 K 2 S 2 O 8 , 21 peroxides, 22 I 2 /TBHP 23 and TBAI/TBHP 24,25 systems. It is well-known that oxygen is an ideal environmentally friendly oxidant, which offers fascinating industrial and academic prospects.…”

Copper‐Catalyzed Electrophilic Cyclization of N‐Propargylamines with Sodium Sulfinate for the Synthesis of 3‐Sulfonated Quinolines

“…On the basis of the obtained experimental resultsa nd the previousr eports, [14] ap ossible mechanism for copper-catalyzed electrophilic cyclization of N-propargylamines is proposed in Scheme 4. Cu I could be easily oxidized to Cu II in the presence of TBHP.T hen the coordination of copper(II) with sodium ben-…”

“…In view of the solubilityo fs odium benzenesulfinate 2a in the organic solvent, 5equiv.H OAc were added into the reactiona nd the yield could be increased to 45 %( entry 13). Duringt he examination of solvent effect, dichloroethane (DCE) was found to be the most suitable solvent (53 %, entries [14][15][16]. To further enhancet he reaction yield, some phase-transfer catalysts were evaluated, including (nBu) 4 NOAc,( nBu) 4 NF,( nBu) 4 NBr and (nBu) 4 NHSO 4 (entries [17][18][19][20].…”

“…Recently, the oxidative cyclization of N ‐propargylamines has been proved to be an efficient and facile route for diversity‐oriented synthesis of 3‐quinoline derivatives . In 2016, Zhao group reported a cascade synthesis of 3‐arylsulfonylquionlines through tert ‐butyl hydroperoxide (TBHP)‐mediated cyclization between N ‐propargylamines and arylsulfonohydrazides . With the visible‐light‐induced cyclo‐addition strategy, Zhang and Li groups, respectively developed radical cyclization of N ‐propargylamines using diaryliodonium salts with sulfur dioxide and sulfinic acids as sulfonyl radical precursors (Scheme ).…”

Recent Advances in Metal-Free Quinoline Synthesis

“…The oxidative cyclization reaction is promoted by tert-butyl hydroperoxide (TBHP) and a single electron mechanistic pathway is proposed to deliver the products in good to excellent yields. Finally, a very recent contribution from Tang et al [54] describes the synthesis of 3-arylsulfonylquinolines 95 from N-propargyl aromatic amines 96 and arylsulfonylhydrazides 97 (Figure 41). The oxidative cyclization reaction is promoted by tert-butyl hydroperoxide (TBHP) and a single electron mechanistic pathway is proposed to deliver the products in good to excellent yields.…”