Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides.

Rongxiang Chen,Shaohong Xu,Lantao Liu,Kaikai Wang,Fumin Shen,Zhanyong Wang,Canran Xu

doi:10.3390/molecules26185551

Rongxiang Chen, Shaohong Xu + Show 5 more

Open Access

https://doi.org/10.3390/molecules26185551

Copy DOI

Abstract

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.

Highlights

Sulfonyl chlorides are the most prevalent reagents for the installation of the sulfonyl protecting group [1], which can be converted into numerous sulfonyl derivatives [2,3,4,5,6], undergo diverse desulfitative cross-couplings [7,8], and serve as arylating agents [9,10,11,12,13]
Chlorination with different sulfur compounds [29,30,31,32] or Grignard reactions [33] have been developed as efficient methods for the synthesis of sulfonyl chlorides
Magnotta reported a simple strategy for the synthesis of sulfonyl bromides from sulfonyl hydrazides with bromine (Scheme 1c) [37]

Summary

Introduction

Sulfonyl chlorides are the most prevalent reagents for the installation of the sulfonyl protecting group [1], which can be converted into numerous sulfonyl derivatives [2,3,4,5,6], undergo diverse desulfitative cross-couplings [7,8], and serve as arylating agents [9,10,11,12,13] They have been widely used as important building blocks for the manufacture of elastomers, pharmaceuticals, dyes, detergents, ion exchange resins, and herbicides [14,15,16]. In 2017, Montelongo’s group developed an elegant strategy for the synthesis of sulfonyl chlorides and bromides by the oxidation of thiols using NCS/NBS-iPrOH as an oxyhalogenation reagent (Scheme 1a) [34]. Magnotta reported a simple strategy for the synthesis of sulfonyl bromides from sulfonyl hydrazides with bromine (Scheme 1c) [37] This strategy represents a highly valuable synthetic tool but leaves ample opportunities to develop more green and gentle reaction. Inspired by the work of Cornella, we first evaluated the reaction usingWMe cgcoComml2mmaesentnhcceeeddhoaoulourgrsetsuntdusyoduybrycbieynivniensCvteHigsa3tCitgiNnagtian4tg-rmo4eo-tmhyetltebhmeynlpbzeernaeztuseunrelefsowunilhtfhoyonduhratyzadindrayezc(i1daatea) la(y1nsadt)s aonrhdaadalodhgiaetlinovgesseo;nuhrsocoweuer(2cve)e.r(2,In)n.soIpnaisrppepdirreebdcyiabtbyhletehwfeoowrmrokaroktifoonCf Coorfonrteanlrelgalle,atw,pwereofidfriusrtsctee3vvaaalwuluaaatsteedddetthehceeteredeaicntitohne uresiancgtioMngmCli22xataussrttehhee(Thaablolege1n, esnoturryce1)i.nSCuHbs33eCCqNNueaantttroscormeetneimngpeorfataurlaerwgeithpoauntelanoyf cchatlaolryidstess ofor uanddditthivaetst;hheouwseevoefrC, nuoCal prepsruelctieadblien ftohremgaetnioenraotifotnarogfe3tapartoda u3c8t%3ayiwelads(dTeatbelcete1d, einnttrhiees r2e–a7c)t.ioWnemmfuiixxrtttuhurerere(iTn(Tavbaelbselte1ig, 1ae,tneetdrnytrh1ye). r1Se)u.abcStsuievbqistueyeqnoutfesoncrtrgeasecnnriiecnecgnhoilnfogaridloafersga,ealpanradgnteehlpeoarfnecsehullolotrsfidscuehsglogforeiusdtnedds fttohhuaatnttdNhetChuSast(eNtho-fechCulusoeCroolsfrueCscuucilCntelidmreiisnduetlh)teewdgaeisnnoetphrateitmigoeannloetofra3ptairooanvt aiodf3e83a%a cayotimaelp3d8a(%rTaabyblileeel9d19,%(eTnaytbrieileelds12(,–Te7an)b.trlWeie1es, 2feu–nr7tt)rh.ieeWrs ei8nf–vu1er0st)ht.iegFrautinerdtvheteshrtemigroaetraecd,titvhiteyrroeefapcoltarigcveaitmnyieconcftholorogfraiCdnHeics3,cCahNnlodrwitdhieethsr,eoasntuhdletstrhsseuogrlevgseeunslttesdshutahgmagtpeNsetrCeedSd t(phNra-otcdhNulCoctrSof(soNurm-ccchaintlioiomrnoisdtuoec)vcwianraimosuoidspedt)iemwgaraelsetoosp(ptTirmaobvaliledt1oe,paerncootvrmiedpsea1ar1ac−bo1lm6e)p9. 9Fa%ruarbtyhlieeelr9dm9%(oTrayebi,eltelhde1(,Treeanpbtllraeice1es,e8mn–t1ern0ie)t.soFf8uN–r1Ct0hS)e.rwFmiutohrrtheN,eBtrhmSe(oNrree-pb, lrtaohcmeemoreseupncltaccoinefmimCeHind3teC)oNaflsCwoHistm3hCooNothtwhelriytshporlovotevhniedtrsedshoatlhmveepnteatrsreghdeatpmprropodedruuecdctt pfsorurolmfdoauntciytolnfbotroomvmaatiridiooenu4staodaevtgarareinoesu8(s7T%dabeygleiree1le,dsen((TtTraaibebsllee1111−,, ee1nn6t)tr.ryiFeu1s7r1t)h1. −eH1rm6o)wo. rFeevu,erthrth,eewrremhpelonarceue,mstihneengtrNeopfISNla(cCNeS-mwioiedtnhotsNoufBcNcSinC(NiSm-wbidriotehm) aNossBtuhScec(Nisnu-ibmrsoitdrmaeto)esa,ultshcoceisncmoimroroiedtshep)loyanlpdsroionsvgmidpoeroodtdhtuhlycetpt5ararogvweidtaspedrnootdhtuefoctrtamsrugeeldfto(pnTryaolbdbluerco1t-, smeunildtfroeyn41ya8l a)b.traonm8i7d%e 4yaiealdt a(Tnab8l7e%1,yeinetlrdy(1T7a)b. lHe o1w, eenvetrry, w1h7)e.nHuoswinegvNerI,Sw(Nh-einoduossiuncgciNniImS i(dNe-) iaosdtohseuscucbinsitmraitdee, )thaes cthoerrseuspbsotnrdatien,gthperocdorurcets5paonwdaisnngoptrfoodrumcetd5a(Twabalsen1o,tefnotrrmy e1d8)(.Table 1, eTnatbryle118. )O. ptimization of reaction conditions a

Source

Discussion

Conclusions