transfer of sulfur: from simple to diverse.download.xuebalib.com/3sismsp8nxcn.pdf · doi:...

FOCUS REVIEW

Organosulfur Compounds

Hui Liu, Xuefeng Jiang* &&&&—&&&&

Transfer of Sulfur: From Simple toDiverse

C�S the day : Organosulfur com-pounds, including a wide range of nat-ural products and drugs, have receivedconsiderable attention over the pastfew decades, owing to their remarkablybioactivity in biochemistry and medici-nal chemistry. Numerous excellent sul-furation agents have been developedfor the construction of C�S bonds. Inthis review, the various strategies forC�S bond formation are collectedaccording to their sulfuration agents.

Chem. Asian J. 2013, 00, 0 – 0 � 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim1 &&

These are not the final page numbers! ��

FOCUS REVIEW

www.interscience.wiley.com

DOI: 10.1002/asia.201300636

Transfer of Sulfur: From Simple to Diverse

Hui Liu[a, b] and Xuefeng Jiang*[a]

Chem. Asian J. 2013, 00, 0 – 0 � 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim2&&

�� These are not the final page numbers!

www.chemasianj.org Hui Liu and Xuefeng Jiang

Abstract: The introduction of sulfur atoms onto targetmolecules is an important area in organic synthesis, in par-ticular in the synthesis of pharmaceutical compounds, anda wide variety of sulfuration agents have been developedfor thionation reactions over the past few decades. In thisFocus Review, we collect and summarize the C�S bond-

formation reactions that have been used to construct C�Sbonds in natural products and pharmaceutical compounds.

Keywords: cross-coupling · drug design · heterocycles ·natural products · sulfur

1. Introduction

Sulfur-containing architecturesserve important functions ingeneral organic synthesis, aswell as applications in the phar-maceutical industry and in ma-terials science.[1] Organosulfurcompounds widely exist indrugs and natural products.Penicillins, as well-knownsulfur-containing antibiotics, arehistorically significant drugsthat have been effective againstsyphilis or infections that arecaused by staphylococci andstreptococci. Although somekinds of bacteria are resistantto Penicillin and its derivatives,they are still popular antibioticsin the treatment of bacterial in-fections that are caused by sus-ceptible, usually gram-positive,organisms.[2] Prevacid isa proton-pump inhibitor (PPI) that inhibits the stomach’sproduction of gastric acids.[3] Seroquel is an atypical antipsy-chotic that has been approved for the treatment of schizo-phrenia, bipolar disorder, and, in the Seroquel XR version,along with an SSRI (selective serotonin reuptake inhibitor),to treat major depressive disorders.[4] Epipolythiodiketopi-perazine alkaloids, such as (�)-acetylaranotin, which exhibita wide range of biological activities, including antiviral, anti-bacterial, antiallergic, antimalarial, and cytotoxic properties,contain a core 2,5-diketopiperazine structural motif.[5]

Organosulfur compounds have received considerable at-tention in recent years and numerous methods for the con-

struction of C�S bonds have been developed.[1,6] Thiols, sul-fides, and their oxidized derivatives are widely utilized insynthetic transformations to afford organosulfur compounds.However, they have been known to act as transition-metal-catalyst poisons, owing to their strong coordinating proper-ties.[7] In recent decades, some of these problems have beenovercome with the developments in organometallic chemis-try and many excellent procedures have been developed forC�S bond formation.

With the tremendous developments in C�S bond forma-tion, numerous sulfuration agents have been used as thesulfur source. Thiols have been the most-popular reagents inthe construction of C�S bonds, such as through SN2 replace-ment and cross-coupling reactions.[6,8] However, most thiolshave unpleasant odors during these processes, which impedetheir application. Sulfur powder (S8), which is abundant andsmell-free in nature, has been extensively investigated forintroducing sulfur atoms into organic molecules. A wide va-riety of inorganic metal sulfides, such as sodium sulfide, po-tassium sulfide, sodium thiosulfate, Na2S4, sodium bisulfide,and potassium thiocyanate, have been successfully used asa sulfur source. In addition, thiourea, thioacetate, and theirderivatives were also quite efficient in providing sulfur

[a] Dr. H. Liu, Prof. X. JiangShanghai Key Laboratory of Green Chemistry andChemical Processes, Department of ChemistryEast China Normal University3663 North Zhongshan Road, Shanghai 200062 (P. R. China)Fax: (+86) 21-52133654E-mail : [email protected]

[b] Dr. H. LiuSchool of Chemical EngineeringShandong University of TechnologyZibo, 255049 (P. R. China)




atoms. Some reagents have been developed for the thiona-tion of carbonyl compounds, such as Lawesson’s reagent,Belleau’s reagent, etc. In this Focus Review, we have sum-marized the area of C�S bond construction with differentsulfuration agents.

2. C�S Bond Construction by Different SulfurationAgents

2.1. S8 as a Sulfuration Agent

Sulfur powder (S8), as an abundant elemental substance, hasbeen widely applied for introducing sulfur atoms onto mole-cules.

Methylenecyclopropanes (MCPs), which contain high in-tramolecular ring strain and high reactivity, can undergoa direct [3+2] radical cycloaddition reaction with elementalsulfur under thermal conditions, thus providing an efficientsynthesis of methylene-1,2-dithiolane derivatives(Scheme 1).[9] The Z/E selectivity of unsymmetrical MCPs

seems to correlate closely with the steric and electronicproperties of the substituents. In general, monosubstitutedMCPs give higher Z/E selectivities than disubstituted ones(Scheme 1). Bulky groups with higher steric asymmetry andthose that contain electron-withdrawing groups could resultin higher Z/E selectivities.

A CuI-catalyzed oxidative trifluoromethylthiolation of ar-ylboronic acids by using (trifluoromethyl)trimethylsilaneand sulfur at room temperature was developed for the syn-thesis of aryl trifluoromethyl thioethers (Scheme 2).[10] Anorganocopper(II) disulfide complex, as observed by Karlinand co-workers,[11] has been proposed as the key intermedi-ate in the catalytic cycle (Scheme 2). According to the two

possible pathways, copper(V) or (VI) complexes could beformed, which both lead to the same product, ArSCF3.

A comparative study between terminal alkynes and aryl-boronic acid was reported as a metal-free oxidative trifluor-omethylthiolation reaction;[12] the reaction mechanism isshown in Scheme 3. In the presence of potassium fluoride,

Abstract in Chinese:

Xuefeng Jiang received his BS degreefrom Northwest University (China) in2003, after which he pursued his PhDstudies with Professor Shengming Ma atthe Shanghai Institute of Organic Chemis-try (SIOC), the Chinese Academy of Sci-ences. From 2008 to 2011, he was a Post-doctoral Researcher under the guidanceof Professor K. C. Nicolaou at TheScripps Research Institute (TSRI) in thefield of natural product total synthesis. Heis currently a Professor at East ChinaNormal University and his research inter-ests are in methodology-oriented totalsynthesis.

Hui Liu received his BS degree in Chemi-cal Engineering and Technology at QufuNormal University (China) in 2006. In2012, he received his PhD in AppliedChemistry from the East China Universityof Science and Technology under the su-pervision of Prof. Limin Wang and Prof.Xiaofeng Tong. He is now undertakingPostdoctoral Studies at East ChinaNormal University with Prof. XuefengJiang.

Scheme 1. ACHTUNGTRENNUNG[3+2] Radical cycloaddition reaction of S8 to methylenecyclo-propanes by Xu, Yu, and co-workers.[9] DCE =1,2-dichloroethane.

Scheme 2. CuI-catalyzed trifluoromethylthiolation of arylboronic acids byQing and co-workers.[10]




sulfur powder, and DMF, (trifluoromethyl)trimethylsilanecould be converted into the active trifluoromethyl sulfideanion species (possibly KSCF3), which could then react withphenylacetylene by using elemental sulfur as an oxidant toproduce the trifluoromethylthiolated products.

Copper(I)-trifluoromethylthiolate complexes, which wereformed from copper fluoride, (trifluoromethyl)trimethylsi-lane, and sulfur powder, reacted with a wide range of aryland heteroaryl halides to produce aryl trifluoromethyl thio-ethers in modest-to-excellent yields (Scheme 4).[13] Bipyri-dine-ligated Cu complexes were shown to be effective tri-fluoromethylthiolation reagents.

The [RhH ACHTUNGTRENNUNG(PPh3)4]-catalyzed synthesis of bis(4-substituted2,3,5,6-tetrafluorophenyl) sulfides by using substituted pen-tafluorobenzenes and S8 was developed by Arisawa, Yama-guchi, and co-workers through C ACHTUNGTRENNUNG(sp2)�F bond activation(Scheme 5).[14]

The Cu-catalyzed three-component (o-iodoaniline, an al-dehyde, and sulfur powder) synthesis of substituted benzo-thiazoles in a simple one-pot procedure has been developed

(Scheme 6).[15] Water is used as the solvent in a simple andenvironmentally friendly procedure. High yields and excel-lent tolerance of a diverse range of functional groups forconstructing benzothiazoles make this method highly attrac-tive.

Very recently, Zhou and co-workers developed an effi-cient procedure for the preparation of disulfides from arylhalides and sulfur in water (Scheme 7).[16]

Another CuI-catalyzed preparation of aryl thiols fromaryl iodides and sulfur was achieved in the presence of po-tassium carbonate at 90 8C (Scheme 8).[17] The aryl thiolswere obtained in good-to-excellent yields by treating thecoupling mixture with sodium borohydride or triphenylphos-phine. A wide range of substituted aryl thiols that containedmethoxy, hydroxy, carboxylate, amido, keto, bromo, andfluoro groups were synthesized by using this procedure.

Very recently, Childers et al. reported a new and conven-ient multi-component reaction for the synthesis of fully sub-stituted thiazoles (Scheme 9).[18] Many examples were

Scheme 3. Metal-free oxidative trifluoromethylthiolation by Qing and co-workers.[12]

Scheme 4. Bipyridine-ligated Cu-complex-mediated formation of Ar�SCF3 compounds by Weng, Huang, and co-workers.

[13] bpy=2,2’-bipyri-dine, dmbpy=4,4’-dimethyl-2,2’-bipyridine, dtbpy =4,4’-di-tert-butylbipyr-idine, phen =1,10-phenanthroline.

Scheme 5. Rh-catalyzed C�F activation and C�S bond formation by Ari-sawa, Yamaguchi, and co-workers.[14] dppBz =1,2-bis(diphenylphosphi-no)benzene.

Scheme 6. Cu-catalyzed synthesis of substituted benzothiazoles by Zhouand co-workers.[15]

Scheme 7. Synthesis of disulfides by Zhou and co-workers.[16] TBAF = tet-rabutylammoniumfluoride.




tested; however, the transformation was not practical, owingto the isolation of the products in low yields (0–44 %).

Eftekhari-Sis et al. developed an efficient synthesis of a-ketothioamides through a Willgerodt–Kindler reaction witharylglyoxal hydrates, secondary amines, and elemental sulfurunder neat conditions (Scheme 10).[19]

Natural products epidithiodiketopiperazines (ETPs) area large and structurally diverse family of biologically activemolecules. One of the features of ETPs is their dithiolbridge. In the total synthesis of epicoccin G, Nicolaou et al.used elemental sulfur to construct the dithiol bridge(Scheme 11).[20] S8 needed to be pretreated with 3.0 equiva-lents of sodium hexamethyldisilazide (NaHMDS) at ambienttemperature, followed by the sequential addition of com-pound 28 and an additional two equivalents of NaHMDS,thus providing a mixture of oligosulfenylated compounds 29.Then, compound 29 was treated with sodium borohydrideand KI3, thus leading to the corresponding epidithiodiketo-piperazine (30), which could be converted into compound31 by reduction with sodium borohydride and quenchingwith methyl iodide.

In the total synthesis of (�)-acetylaranotin, Reisman andco-workers employed S8 to afford the dithiol structure(Scheme 12).[21] Compound 34 was treated with NaHMDS

and S8 to give tetrasulfide 35. Then, compound 35 was pro-tected by using acetyl chloride to form the diacetate, whichwas sequentially reduced by using propanedithiol and trie-thylamine in MeCN and aerobic oxidation of the resultingdithiol delivered the natural product (36).

Nicolaou et al. developed an improved method for thesulfenylation of 2,5-diketopiperazines that was based on the

Scheme 8. Cu-catalyzed preparation of aryl thiols by Jiang and Ma.[17]

Scheme 9. Base-mediated synthesis of substituted thiazoles by Childerset al.[18]

Scheme 10. Synthesis of a-ketothioamides by Eftekhari-Sis et al.[19]

Scheme 11. Construction of C�S bonds in the synthesis of epicoccin G byNicolaou et al.[20]

Scheme 12. Construction of C�S bonds in the synthesis of (�)-acetylara-notin by Reisman and co-workers.[21] DMAP =4-dimethylaminopyridine.




use of alkali-metal-hexamethyldisilazide bases (i.e.,LiHMDS, NaHMDS, and KHMDS) and sulfur to prepareepidithio-, epitetrathio-, and bis-(methylthio)diketopipera-zines (Scheme 13).[22] In the presence of NaHMDS, sulfurwas converted into compound 37, which was transformedinto compound 38 with three equivalents of NaHMDS. S4-bridged intermediate 40 was generated from compounds 39and 38 in the presence of NaHMDS. Compound 41 could beobtained by reduction with sodium borohydride and oxida-tion with KI3. When the reduction mixture was treated withmethyl iodide, product 42 was generated (Scheme 13).

2.2. Na2S/K2S/NaHS/H2S/Na2S4

Metal sulfides are also a clean and sustainable thiol source.2-Alkynyl-1-chloro- and 1-alkynyl-2-chloroanthraquinones,which was prepared by using Sonogashira reactions, cyclizedwith Na2S to afford anthra ACHTUNGTRENNUNG[1,2-b]thiophene-6,11-diones andanthra ACHTUNGTRENNUNG[2,1-b]thiophene-6,11-diones, respectively(Scheme 14).[23]

Benzo[b]thiophene and its derivatives were synthesizedfrom o-halo-substituted ethynylbenzenes in one pot(Scheme 15).[24] The parent compound and its alkyl- andphenyl-substituted derivatives, as well as benzo[1,2-b:4,5-b’]dithiophenes and benzo[1,2-b:3,4-b’:5,6-b’’]trithiophenes,can be prepared in good-to-excellent yields.

The CuI-catalyzed coupling reaction of aryl halides withsodium sulfide has been developed for the synthesis of sub-stituted benzothiazoles (Scheme 16).[25] Extensive scope andmild reaction conditions make this approach a good choicefor producing substituted benzothiazoles. A tentative reac-tion scheme is shown in Scheme 16: After the oxidative ad-dition of CuI to form intermediate 57, intermediate 58 could

be formed through ligand exchange with sodium sulfide,which could then undergo reductive elimination to produceintermediate 59 and regenerate CuI. The desired product(56) could be obtained from the intramolecular condensa-tion of compound 59. Compound 60 was isolated by trap-ping the coupling mixture with methyl iodide, which indicat-ed that intermediate 59 had formed.

The CuI-catalyzed double C�S bond formation of 1,4-di-halides with sodium sulfide has been developed for the se-lective synthesis of 2-trifluoromethyl benzothiophenes(Scheme 17).[26] The trifluoromethyl group played an essen-tial role in this transformation and substrates without a tri-fluoromethyl group gave low yields of the products.

Azizi, Saidi, and co-workers developed a ring-opening re-action of epoxides with sodium sulfide by using water as thesolvent (Scheme 18)[27] and various substituted bis(hydrox-yethyl) thioethers were obtained in high yields.

Scheme 13. An improved method for the sulfenylation of 2,5-diketopiper-azines by Nicolaou et al.[22] TMS= trimethylsilyl.

Scheme 14. Na2S-mediated cyclization of 2-alkynyl-1-chloro- and 1-alkyn-yl-2-chloroanthraquinones by Shvartsberg and co-workers.[23]

Scheme 15. Synthesis of benzo[b]thiophene derivatives mediated by Na2Sby Takimiya and co-workers.[24] NMP= N-methylpyrrolidone.




Substituted thiophenes were synthesized through a Cu-catalyzed tandem S-alkenylation of potassium sulfide with1,4-diiodo-1,3-dienes (Scheme 19).[28] Di-, tri-, and tetrasub-stituted thiophenes were obtained in excellent yieldsthrough this approach.

Substituted benzothiazoles were synthesized by CuI-cata-lyzed thiolative annulations of 1,4-dihalides by using sodiumbisulfide as a sulfur source (Scheme 20).[26]

The first conversion of alcohols into thiols catalyzed bytransition metal was reported by Alper and Sibtain in 1988(Scheme 21).[29] In the present of Co2(CO)8 and hydrogen

sulfide, hydroxy groups could be converted into thiols inmoderate yields (Scheme 21).

An approach to construct the disulfide bridges in naturalproducts by using condensed hydrogen sulfide, BF3·OEt2,and iodine has been widely explored.[30–32] In the first totalsynthesis of (+)-chaetocin, Sodeoka and co-workers em-ployed this approach to introduce the key disulfide bridge inthe last step (Scheme 22).[30] The reaction was carried out inthe presence of BF3·OEt2 at �78 8C in 44 % yield. Overman

Scheme 16. CuI-catalyzed synthesis of substituted benzothiazoles by Maet al.[25]

Scheme 17. CuI-catalyzed double C�S bond formation from 1,4-dihalidesby Zhang, Li, and co-workers.[26]

Scheme 18. Na2S-mediated ring-opening of epoxides by Azizi, Saidi, andco-workers.[27]

Scheme 19. Cu-catalyzed synthesis of substituted thiophenes by Xi andco-workers.[28]

Scheme 20. Cu-catalyzed double C�S bond formation with sodium bisul-fide Zhang, Li, and co-workers.[26]

Scheme 21. Co-catalyzed thionation of alcohols by Alper and Sibtain.[29]

Scheme 22. Construction of the disulfide bridge in the synthesis of(+)-Chaetocin by Sodeoka and co-workers.[30] TBS = tert-butyldimethyl-silyl, Boc= tert-butoxycarbonyl.




and co-workers employed the same strategy in the synthesisof (+)-gliocladine C and oxygen was used instead of iodineas the sole oxidant (Scheme 23).[31] Very recently, in the syn-thesis of di(methylthio)ethers of plectosphaeroic acid B byJabri and Overman, 80–90 % yields were obtained under theconditions of hydrogen sulfide/BF3·Et2O, followed by methyliodide/potassium carbonate (Scheme 24).[32]

In the synthesis of (+)-11,11’-dideoxyverticillin A by Mo-vassaghi and co-workers, the combination of hydrogen sul-fide and hafnium triflate could convert the OH group intoSH at �78 8C (Scheme 25).[33] The benzenesulfonyl groups ofcompound 80 were removed by Na/Hg to afford compound81, which could be convertedinto compound 82 in the pres-ence of hydrogen sulfide andhafnium triflate. Oxidation ofthe tetrathiols with potassiumtriiodide resulted in (+)-11,11’-dideoxyverticillin A in lowoverall yields (2–15 %, threesteps). Overman and Sato usedscandium trifluoromethanesul-fonate, hydrogen sulfide, andoxygen oxidation to constructthe disulfide bridge(Scheme 26).[34] Dithiol inter-mediate 85, which was pro-duced from triacetate 84 andexcess hydrogen sulfide, cata-lyzed by scandium triflate,could be converted into epidi-thiodioxopiperazine product 86upon exposure to oxygen in37 % yield. Notably, MeCN sol-vent was crucial for achieving

this transformation; CH2Cl2, benzene, Et2O, or nitromethanecould not give the desired product.

Kim and Movassaghi developed the selective conversionof OH groups into SH groups by using hydrogen sulfide and

Scheme 23. Construction of the disulfide bridge in the synthesis of glio-cladine C by Overman and co-workers.[31]

Scheme 24. Construction of the C�S bond in plectosphaeroic acid B byJabri and Overman.[32]

Scheme 25. Construction of the disulfide bridge in the synthesis of (+)-11,11’-dideoxyverticillin A by Movassa-ghi and co-workers.[33]




trifluoroacetic acid in nitromethane (Scheme 27).[35] Threenatural products, (+)-chaetocin A, (+)-chaetocin C, and(+)-12,12’-dideoxychetracin A, were achieved by using thecorresponding Ph3C-X-Cl species.

A concise asymmetric synthesis of (�)-neothiobinuphari-dine in eight steps has been reported by Jansen and

Shenvi.[36] trans-Quinolizidine N-oxide 95 was converted intothe desired product (98) in an efficient manner, by usingNa2S4·H2O for constructing the tetrahydrothiophene ring asa key step (Scheme 28).

2.3. Sulfuration Agents that Contain a Leaving Group(AcSR/KSCN/R2N-SR/R3SiSH/Xanthates/Na2S2O3)

Potassium thioacetate was a good coupling partner for intro-ducing thioacetate groups onto target molecules. The prepa-ration of S-aryl thioacetates through cross-coupling reac-tions of aryl bromides or aryl triflates with potassium thioa-cetate was developed by using Pd as a catalyst(Scheme 29).[37] Then, the S-aryl thioacetates could be trans-ferred onto various sulfur compounds, such as ArSH, ArSR,ArSCl, and ArSOCl, in a single step.

Symmetrical and unsymmet-rical diaryl sulfides were syn-thesized by employing potassi-um thioacetate with aryl iodidesand aryl bromides under Pdcatalysis (Scheme 30).[38] Highyields, excellent tolerance tofunctional groups, and smell-free reactants made thismethod highly practical.

A one-pot procedure for thepreparation of benzyl aryl thio-ethers was developed by usinga benzyl halide, potassium thio-acetate, and an aryl bromide(Scheme 31).[39] The benzyl thi-oacetates were formed in situand coupled with ArBr, cata-lyzed by Pd/XPhos.

An efficient, Cu-catalyzedprocedure for the synthesis ofdiaryl sulfides has been de-scribed by Zhou and co-work-ers (Scheme 32).[40] Aryl thio-cyanate 114 was formed in thefirst step, followed by hydroly-sis into thiolate ion 115, whichreacted with the aryl halide toafford the C�S coupling prod-uct.

The Cu-catalyzed reaction ofo-halobenzamide derivativeswith potassium thiocyanate inwater was demonstrated to syn-thesize benzisothiazol-3 ACHTUNGTRENNUNG(2H)-one derivatives througha tandem reaction with S�Cand S�N bond formations(Scheme 33).[41]

Cu-catalyzed C�S bond for-mation with boronic acids by

Scheme 26. Construction of a disulfide bridge by using H2S and O2 byOverman and Sato.[34]

Scheme 27. Construction of disulfide, trisulfide, and tetrasulfide bridges by Kim and Movassaghi.[35] TFA = tri-fluoroacetic acid.




using N-thio(alkyl, aryl, heteroaryl) imides as the RS donorwas described by Srogl and co-workers (Scheme 34).[42] Ac-cording to the proposed mechanism, CuIII species were gen-erated by the oxidative addition of CuI to the S�N bond,

Scheme 28. Construction of the tetrahydrothiophene ring by using Na2S4by Jansen and Shenvi.[36]

Scheme 29. Pd-catalyzed preparation of S-aryl thioacetates by Lai andBackes.[37] dba=dibenzylideneacetone.

Scheme 30. Pd-catalyzed synthesis of diaryl sulfides by Lee and co-work-ers.[38] dppf =1,1’-bis(diphenylphosphino)ferrocene.

Scheme 31. One-pot synthesis of benzyl aryl thioethers by Wager andDaniels.[39] XPhos =2-dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl.

Scheme 32. Cu-catalyzed synthesis of diaryl sulfides by using potassiumthiocyanate by Zhou and co-workers.[40]

Scheme 33. Cu-catalyzed synthesis of benzisothiazol-3 ACHTUNGTRENNUNG(2 H)-one deriva-tives by Chen, Xi, and co-workers.[41] DABCO=1,4-diazabicyclo-ACHTUNGTRENNUNG[2.2.2]octane.Scheme 34. Cu-catalyzed C�S bond formation by using N-thioimides bySrogl and co-workers.[42]




followed by transmetalation from boron to Cu and subse-quent C�S reductive elimination to give the coupling prod-ucts.

Shi and co-workers developed an efficient acid-catalyzedregioselective and stereoselective electrophilic sulfetherifica-tion of alkenols, thus providing either the 5-exo or 6-endoproducts depending on the acid catalyst (Scheme 35).[43]

Studies showed the formation of kinetically favored 5-exoproducts with camphorsulfonic acid (CSA) and thermody-namically favored 6-endo products in the presence of strongacids, such as trifluoromethanesulfonic acid (TfOH).

In the synthesis of discorhabdin A by Kita and co-work-ers, the highly strained and unique sulfur-bridged structurewas formed by using potassium thioacetate or p-MeOBnthiol as a sulfuration agent (Scheme 36).[44] Intermediate 133was generated in the presence of 30 % hydrogen bromide inacetic acid, followed by treatment with aqueous methyla-mine to give the desired product (134) in 22 % yield.

The Pd-catalyzed cross-coupling reaction of R3SiSH thiolswith vinyl (or aryl) halides or triflates was developed for theformation of vinyl (or aryl)-silyl-substituted sulfides, whichcould be transformed into unsymmetrical RSR’ sulfidesthrough cross-coupling reactions (Scheme 37).[45]

The [Pd ACHTUNGTRENNUNG(PPh3)4]-catalyzed bis(triisopropylsilyl)disulfidesyn addition to alkynes, followed by methylation for the syn-thesis of syn-bis(methylthio)ethane derivates, was developed

in moderate-to-excellent yields (Scheme 38).[46] The cross-coupling of aromatic and aliphatic triisopropylsilanylsulfanylcompounds was also realized in a Pd-catalyzed reaction andthe products could be transformed into the correspondingsulfonyl chlorides and sulfonamides (Scheme 39).[47]

An efficient route to 2-substituted benzo[b]thiophenesand 2,3,5-trisubstituted thiophenes was achieved througha tandem C�S coupling/heterocyclization reaction from o-al-kynylbromobenzenes (Scheme 40).[48] Selected electrophilesthat were generated in situ could further expand thismethod to prepare highly substituted thiophenes.

Cu catalysis of aryl halides by using potassium ethyl xan-thogenate as a thiol surrogate led to unsymmetrical diarylthioethers (Scheme 41).[49] This reaction is likely to proceedby the xanthate coupling of copper acetate to form the O-

ethyl S-phenyl carbonodi-thioate, which is subsequentlyhydrolyzed and coupled to givethe diaryl thioethers. Copper-oxide nanoparticles have alsobeen successfully applied in thiskind of reaction in DMSO(Scheme 42).[50] The copper-oxide nanoparticles could be re-covered and reused up to fivecycles without loss of activity.

Sodium dimethylcarbamodi-thioate was also used in the for-mation of C�S bonds with aryliodides and vinyl bromidesunder Ullmann coupling condi-tions (Scheme 43).[51] Both elec-tron-deficient and -rich aryl io-

Scheme 35. Acid-catalyzed sulfetherification of alkenols by Shi and co-workers.[43]

Scheme 36. Construction of a sulfur-bridged ring by Kita and co-workers.[44]

Scheme 37. Pd-catalyzed cross-coupling of R3SiSH with halides.[45]

Scheme 38. Pd-catalyzed synthesis of syn-bis(methylthio)ethane deriva-tives.[46]




dides and sterically hindered vinyl bromides were well-toler-ated in this system.

Ma et al. reported the C�S bond-formation reaction of1,2-allenyl sulfones with bromine, followed by sequentialtreatment with water and saturated sodium thiosulfate(Scheme 44).[52] A variety of 1-sulfonyl alkylidenethiiraneswith high regio- and stereoselectivity could be obtained byusing this approach. A proposed mechanism is shown inScheme 44. Five-membered-ring intermediate 167 could be

formed by the electrophilic addition of Br2 to allene 165 inMeCN. Then, compound 167 was attacked by S2O3

2� toafford acyclic intermediate 168,which could release the sulfurtrioxide, thereby resulting inthe formation of compound169. After intramolecular con-jugated addition and elimina-tion, the desired product (166)was obtained.

Very recently, Jiang and co-workers developed a Pd-cata-lyzed double C�S bond forma-tion by using sodium thiosulfate

as a sulfuration agent (Scheme 45).[53] This method providesan efficient method for the synthesis of substituted 1,4-ben-zothiazine derivatives, which are structural elements in a lotof pharmaceutically active compounds and natural products.

Scheme 39. Pd-catalyzed synthesis of sulfonamides by Gareau et al.[47]

Scheme 40. Pd-catalyzed synthesis of thiophenes by Sanz and co-workers.[48] Xantphos =4,5-bis(diphenylphos-phanyl)-9,9-dimethylxanthene, TIPS = triisopropylsilyl.

Scheme 41. Cu-catalyzed synthesis of diaryl thioethers by using xan-thogenate by Prasad and Sekar.[49]

Scheme 42. CuO-nanoparticle-catalyzed synthesis of diaryl thioethers byAkkilagunta and Kakulapati.[50]

Scheme 43. CuI-catalyzed C�S bond formation by using sodium dime-thylcarbamodithioate by Liu and Bao.[51]

Scheme 44. Synthesis of 1-sulfonyl alkylidenethiiranes by using Na2S2O3by Ma and co-workers.[52]




Bis(phenylsulfonyl)sulfide was used as an electrophilic re-agent in the synthesis of unsymmetrical and symmetricalDTHAs through intramolecular cyclization reactions(Scheme 46).[54] Two types of dicarbanions could be formedunder four different reaction conditions, that is, nBuLi/Et2O,nBuLi/THF, sBuLi/Et2O, and tBuLi/Et2O, and quenchedwith bis(phenylsulfonyl)sulfide to generate symmetrical andunsymmetrical DTHAs.

2.4. RSCF3

Buchwald and co-workers reported a general method forthe Pd-catalyzed Ar�SCF3 bond-forming reaction by usingAgSCF3 as a SCF3 source (Scheme 47).

[55] Heteroaryl bro-mides, such as indoles, pyridines, quinolines, thiophenes, andfurans, were all well-tolerated in this transformation. How-

ever, aryl chlorides or aryl tri-flates could not be convertedinto their corresponding prod-ucts.

The trifluoromethylthiolationof aryl iodides and aryl bro-mides catalyzed by a nickel-bi-pyridine complex was realizedby using [NMe4]

+ ACHTUNGTRENNUNG[SCF3]� asa sulfuration agent(Scheme 48).[56] This procedurewas performed at room temper-ature and both aryl iodides andaryl bromides could be trans-formed into their correspondingproducts. Aryl chlorides wereunreactive toward this process,even at high temperatures.

The allylic trifluoromethylth-iolation of allyl silanes, promot-ed by acetyl chloride with tri-fluoromethanesulfanamide, has

been demonstrated (Scheme 49).[57] Acetyl chloride was ob-served to play an important role as an acidic initiator in thistrifluoromethylthiolation reaction.

Scheme 45. Synthesis of 1,4-benzothiazine derivatives by using Pd/Na2S2O3 by Jiang and co-workers.[53]

TBAB= tetrabutylammoniumbromide.

Scheme 46. Synthesis of DTHAs by Wang and co-workers.[54] DTHA =di-thienoheteroaromatic rings.

Scheme 47. Pd-catalyzed formation of Ar�SCF3 compounds by Buchwaldand co-workers.[55]

Scheme 48. Ni-catalyzed Ar�SCF3 bond formation by Zhang and Vicic.[56]cod=1,5-cyclooctadiene.




Another Cu-catalyzed trifluoromethylthiolation has beendeveloped by Daugulis and co-workers by using (CF3S)2(Scheme 50).[58] This transformation displays high selectivitytoward ortho-C�H bonds. It is a new and straightforwardmethod for the preparation of ArSCF3.

2.5. ArSO2Na/R2SO2NHNH2

Copper complexes are efficient in promoting C�S bond for-mation through the coupling of ArX with sulfonic acid salts.The formation of copper-trifluoromethanesulfonate-cata-lyzed sulfones (ArSO2R) was achieved by ArI and R�SO2Na (Scheme 51).

[59a] Neither aryl bromides nor arylchlorides could react in this system. When 3-methoxy-3-oxo-propane-1-sulfinate was used, aryl halides could undergo theC�S bond formation in the presence of three equivalents ofCuI.[59b]

The C�S bond formation of aryl halides with sulfinic acidsalts, catalyzed by CuI/l-proline sodium salt, was carried out

to give the corresponding aryl sulfones in good-to-excellentyields (Scheme 52).[60] A wide range of functional groups, in-cluding hydroxy, amino, acetanilide, ketone, ester, and ni-trile groups, were well-tolerated.

ArX or vinyl bromide were converted into the corre-sponding sulfones with CuI and RSO2Na (Scheme 53).

[61]

Both aryl iodides and aryl bromides gave the desired prod-ucts in moderate-to-high yields.

Tang and Tian developed an iodine-catalyzed sulfenyla-tion reaction of indoles by using sulfonyl hydrazides as a sul-furation agent through the cleavage of S�O and S�N bonds(Scheme 54).[62] A range of aryl-, heteroaryl-, and alkyl-sul-fonyl hydrazides was smoothly converted into their corre-sponding indole thioethers in moderate-to-excellent yieldswith extremely high regioselectivity. A plausible mechanismwas proposed in Scheme 54. In the presence of I2, sulfonylhydrazide was converted into compound 207, which wassubsequently transformed into diazonium 209 with an addi-tional mole of I2. Then, intermediate 209 reacted withindole to afford the corresponding products (205,Scheme 54).

Keim and Herwig demonstrated a Pd-catalyzed hydrosul-fination of alkenes from alkenes, sulfur dioxide/hydrogen,and [Pd ACHTUNGTRENNUNG(dppp)ACHTUNGTRENNUNG(MeCN)2]ACHTUNGTRENNUNG[BF4]2 at 80 8C (Scheme 55).[63] S-alkyl alkanethiosulfonates and sufonic acid can be synthe-sized by using this method.

Scheme 49. CH3COCl-promoted trifluoromethylthiolation withPhNHSCF3 by Qing and co-workers.

[57] DMAc =N,N-dimethylacetamide.

Scheme 50. Cu-catalyzed trifluoromethylthiolation of C�H bonds byDaugulis and co-workers.[58]

Scheme 51. Cu-mediated formation of ArSO2R sulfones by Baskin andWang.[59]

Scheme 52. CuI/l-proline-sodium-salt-catalyzed formation of ArSO2Rsulfones by Zhu and Ma.[60]

Scheme 53. CuI-catalyzed formation of sulfones by Ma and Wang.[61]




2.6. NH2CSNH2/CS2

Thiourea is another widely used sulfuration agent in organicsynthesis. Takagi reported the Ni-catalyzed reaction of aryliodides with thiourea to afford S-aryl-isothiuronium iodides(216), which were subsequently hydrolyzed into their corre-sponding aromatic thiols in quantitative yield(Scheme 56).[64] When 2-iodoaniline and thiourea were ap-plied under the same conditions, 2-benzothiazolamines wereobtained in high yields (Scheme 57).[65]

Inspired by the sulfur-atom-transfer mechanism, a CuI-catalyzed synthesis of thioethers from aryl halides and alkyl

bromides was reported by using thiourea as a thiol surrogate(Scheme 58).[66]

A mixture of alkyl halides, thiourea, and electron-defi-cient alkenes in wet PEG 200 produced the related thia-Mi-chael adducts in good-to0excellent yields (Scheme 59).[67a]

This C�S cross-coupling system has been successfully ex-panded to both intra- and intermolecular reactions.[67b, c]

Paradies and co-workers described a Pd-catalyzed methodfor the C�S coupling of aryl bromides and iodides by usingthiourea as a dihydrosulfide surrogate (Scheme 60).[68] Struc-turally important biarylthioethers, benzo[b]thiophenes, andthieno ACHTUNGTRENNUNG[3,2-b]thiophene scaffolds are synthesized in highyields.

The sodium-ethoxide-mediated formation of 2-R-anthra-ACHTUNGTRENNUNG[2,1-b]thiophene-6,11-diones was developed through thedirect C�H activation of peri-R-ethynyl-9,10-anthraquinoneswith thiourea (Scheme 61).[69]

Peng and co-workers developed a new and efficientmethod for the synthesis of 4-sulfanylcoumarins(Scheme 62).[70] 4-Tosyloxycoumarins was subjected to thio-urea and alkyl halides in PEG 200-H2O at room tempera-ture to afford substituted 4-sulfanylcoumarins.

Carbon disulfide, which is quite reactive towards nucleo-philes, has been widely used in the synthesis of organosulfur

Scheme 55. Pd-catalyzed hydrosulfination of alkenes by Keim andHerwig.[63] dppp= 1,3-bis(diphenylphosphino)propane.

Scheme 56. Ni-catalyzed synthesis of aromatic thiols by Takagi.[64]

Scheme 57. Ni-catalyzed synthesis of 2-benzothiazolamines by Takagi.[65]

Scheme 58. CuI-catalyzed synthesis of thioethers by Firouzabadi, Iran-poor, et al.[66]

Scheme 59. Synthesis of sulfanes from thiourea by Firouzabadi, Iranpoor,et al.[67a]

Scheme 54. I2-catalyzed sulfenylation reaction of indoles by Yang andTian.[62]




compounds. The synthesis of a-oxoketene S,S-acetals cata-lyzed by tetrabutylammonium bromide was developed byLiu and co-workers, based on b-dicarbonyl compounds andalkyl bromide by using carbon disulfide as the sulfuration

agent in water at room temperature (Scheme 63).[71] A widerange of b-dicarbonyl compounds have been successfullyconverted into the corresponding products in excellentyields.

The combination of carbon disulfide and diethylin inCHCl3 could form a dithiocarbamic acid salt, which couldreact with carbonyl compounds to prepare gem-bis(dithio-carbamate)s and substituted 2-iminium-1,3-dithietane ringsmediated by BF3·Et2O (Scheme 64).

[72] Because the depro-tection of gem-bis(dithiocarbamate)s with aqueous nitricacid was very simple, this method could be used to protectaldehyde carbonyl groups.

A combination of carbon disulfide and sodium sulfide wasused in the synthesis of b-glycosyl thiol derivatives with high

Scheme 61. NaOEt-mediated formation of C�S bonds by Vasilevsky, Ala-bugin, and co-workers.[69]

Scheme 63. Tetrabutylammonium bromide (TBAB)-mediated synthesisof a-oxoketene S,S-acetals by Liu and co-workers.[71]

Scheme 64. BF3·Et2O-mediated formation of dithiocarbamic acid deri-vates by Halimehjani et al.[72]

Scheme 60. Pd-catalyzed C�S coupling by using thiourea as a dihydrosul-fide surrogate by Paradies and co-workers.[68]

Scheme 62. Synthesis of 4-sulfanylcoumarins from thiourea by Peng andco-workers.[70]




yields and stereoselectivities in one step (Scheme 65).[73] Asodium carbonotrithioate was generated in situ from carbondisulfide (1.5 equiv) and Na2S·9 H2O (2.0 equiv) in DMF atroom temperature and carbon disulfide could act as a leavinggroup to yield the thiols as the final products.

2.7. Thionation of Carbonyl Compounds

The classical method for the thionation of carbonyl com-pounds is sulfuration by using Lawesson’s reagent, whichhas been summarized in several comprehensive reviews.[74]

Other sulfuration agents with similar S-transfer mechanismsfor the thionation of carbonyl compounds, such as Belleau’sreagent, Davy’s reagent, P4S10, etc.,

[75] are summarized inScheme 66.

Conclusions

In conclusion, this Focus Review has compiled the recentadvances in the transfer of sulfur atoms from small sulfur-containing compounds onto natural products and pharma-ceutical candidates. Over the last two or three decades, theimportance of organosulfur compounds in biochemistry andmedicinal chemistry has grown dramatically, owing to therise of medicinal chemistry. As mentioned in this article, nu-merous excellent sulfuration agents have been developedfor the construction of C�S bonds; however, there remain

many challenges in relatedfields and in their application inorganic synthesis. Following thedevelopment of drug discovery,organosulfur compounds haveexhibited promising activities,which make the study of effi-cient sulfuration agents moredesirable. The development ofmore-practical, atom-economi-cal, and environment friendlymethods for the construction ofC�S bonds remains a futurechallenge.

Acknowledgements

Financial support was provided by the NSFC (21272075), the NCET (12-0178), the “Shanghai Pujiang Program” (12J1402500), the “ShanghaiTalent Development Support” (2011022), and the CPSF (2012M520858).

[1] a) Organic Sulfur Chemistry. Theoretical and Experimental Advan-ces, Vol. 19 (Eds: F. Bernardi, I. G. Csizmadia, A. Mangini), Elsevier,Amsterdam, 1985 ; b) E. Block, Reactions of Organosulfur Com-pounds, Academic Press, New York, 1978 ; c) The Chemistry of Or-ganic Selenium and Tellurium Compounds, Vol. 1– 2 (Eds.: S. Patai,Z. Rappoport), Wiley, New York, 1986 –1987; d) OrganoseleniumChemistry: Modern Developments in Organic Synthesis (Ed.: T.Wirth), Springer Verlag, Berlin and New York, 2000 ; e) D. J. Ager,Chem. Soc. Rev. 1982, 11, 493; f) M. D. McReynolds, J. M. Dougher-ty, P. R. Hanson, Chem. Rev. 2004, 104, 2239; g) N. V. Zyk, E. K. Be-loglazkina, M. A. Belova, N. S. Dubinina, Russ. Chem. Rev. 2003, 72,769; h) A. Y. Sizov, A. N. Kovregin, A. F. Ermolov, Russ. Chem. Rev.2003, 72, 357; i) C. Lauterbach, J. Fabian, Eur. J. Inorg. Chem. 1999,1995; j) E. G. Hope, W. Levason, Coord. Chem. Rev. 1993, 122, 109;k) P. I. Clemenson, Coord. Chem. Rev. 1990, 106, 171; l) C. J. Yu, Y.Chong, J. F. Kayyem, M. Gozin, J. Org. Chem. 1999, 64, 2070.

[2] a) L. P. Garrod, Br. Med. J. 1960, 1, 527; b) L. P. Garrod, Br. Med. J.1960, 2, 1695.

[3] S. C. Piscitelli, T. F. Goss, J. H. Wilton, D. T. D’Andrea, H. Gold-stein, J. J. Schentag, Antimicrob. Agents Chemother. 1991, 35, 1765.

[4] M. E. Thase, W. MacFadden, R. H. Weisler, W. Chang, B. Paulsson,A. Khan, J. R. Calabrese, J. Clin. Psychopharmacol. 2006, 26, 600.

[5] a) H. Guo, B. Sun, H. Gao, X. Chen, S. Liu, X. Yao, X. Liu, Y. Che,J. Nat. Prod. 2009, 72, 2115; b) J.-M. Wang, G.-Z. Ding, L. Fang, J.-G. Dai, S.-S. Yu, Y.-H. Wang, X.-G. Chen, S.-G. Ma, J. Qu, S. Xu, D.Du, J. Nat. Prod. 2010, 73, 1240.

[6] I. P. Beletskaya, V. P. Ananikov, Chem. Rev. 2011, 111, 1596.[7] a) L. L. Hegedus, R. W. McCabe in Catalyst Poisoning, Marcel

Dekker, New York, 1984 ; b) A. T. Hutton in Comprehensive Coordi-nation Chemistry, Vol. 5 (Eds.: G. Wilkinson, R. D. Gillard, J. A.McCleverty), Pergamon, Oxford, 1984, p. 1151.

[8] T. Kondo, T. Mitsudo, Chem. Rev. 2000, 100, 3205.[9] L. Yu, Y. Wu, T. Chen, Y. Pan, Q. Xu, Org. Lett. 2013, 15, 144.

[10] C. Chen, Y. Xie, L. Chu, R.-W. Wang, X. Zhang, F.-L. Qing, Angew.Chem. 2012, 124, 2542; Angew. Chem. Int. Ed. 2012, 51, 2492.

[11] M. E. Helton, P. Chen, P. P. Paul, Z. TyeKlar, R. D. Sommer, L. N.Zakharov, A. L. Rheingold, E. I. Solomon, K. D. Karlin, J. Am.Chem. Soc. 2003, 125, 1160.

[12] C. Chen, L. Chu, F.-L. Qing, J. Am. Chem. Soc. 2012, 134, 12454.[13] Z. Weng, W. He, C. Chen, R. Lee, D. Tan, Z. Lai, D. Kong, Y. Yuan,

K.-W. Huang, Angew. Chem. 2013, 125, 1588; Angew. Chem. Int. Ed.2013, 52, 1548.

Scheme 65. One-step synthesis of b-glycosyl thiol derivatives by using CS2 and Na2S by Jana and Misra.[73]

Scheme 66. Sulfuration agents for carbonyl compounds.[74,75]




http://dx.doi.org/10.1039/cs9821100493http://dx.doi.org/10.1021/cr020109khttp://dx.doi.org/10.1070/RC2003v072n09ABEH000794http://dx.doi.org/10.1070/RC2003v072n09ABEH000794http://dx.doi.org/10.1070/RC2003v072n04ABEH000784http://dx.doi.org/10.1070/RC2003v072n04ABEH000784http://dx.doi.org/10.1002/(SICI)1099-0682(199911)1999:11%3C1995::AID-EJIC1995%3E3.0.CO;2-Ehttp://dx.doi.org/10.1002/(SICI)1099-0682(199911)1999:11%3C1995::AID-EJIC1995%3E3.0.CO;2-Ehttp://dx.doi.org/10.1016/0010-8545(93)80044-6http://dx.doi.org/10.1016/0010-8545(60)80003-3http://dx.doi.org/10.1021/jo982392mhttp://dx.doi.org/10.1136/bmj.1.5172.527http://dx.doi.org/10.1136/bmj.2.5214.1695http://dx.doi.org/10.1136/bmj.2.5214.1695http://dx.doi.org/10.1128/AAC.35.9.1765http://dx.doi.org/10.1097/01.jcp.0000248603.76231.b7http://dx.doi.org/10.1021/np900654ahttp://dx.doi.org/10.1021/np1000895http://dx.doi.org/10.1021/cr100347khttp://dx.doi.org/10.1021/cr9902749http://dx.doi.org/10.1021/ol3031846http://dx.doi.org/10.1002/ange.201108663http://dx.doi.org/10.1002/ange.201108663http://dx.doi.org/10.1002/anie.201108663http://dx.doi.org/10.1021/ja027574jhttp://dx.doi.org/10.1021/ja027574jhttp://dx.doi.org/10.1021/ja305801mhttp://dx.doi.org/10.1002/ange.201208432http://dx.doi.org/10.1002/anie.201208432http://dx.doi.org/10.1002/anie.201208432

[14] M. Arisawa, T. Ichikawa, M. Yamaguchi, Org. Lett. 2012, 14, 5318.[15] H. Deng, Z. Li, F. Ke, X. Zhou, Chem. Eur. J. 2012, 18, 4840.[16] Z. Li, F. Ke, H. Deng, H. Xu, H. Xiang, X. Zhou, Org. Biomol.

Chem. 2013, 11, 2943.[17] Y. Jiang, Y. Qin, S. Xie, X. Zhang, J. Dong, D. Ma, Org. Lett. 2009,

11, 5250.[18] K. K. Childers, A. M. Haidle, M. R. Machacek, J. P. Rogers, E.

Romeo, Tetrahedron Lett. 2013, 54, 2506.[19] B. Eftekhari-Sis, S. V. Khajeh, O. B�y�kg�ngçr, Synlett 2013, 977.[20] K. C. Nicolaou, S. Totokotsopoulos, D. Gigu�re, Y.-P. Sun, D. Sarlah,

J. Am. Chem. Soc. 2011, 133, 8150.[21] J. A. Codelli, A. L. A. Puchlopek, S. E. Reisman, J. Am. Chem. Soc.

2012, 134, 1930.[22] K. C. Nicolaou, M. Lu, S. Totokotsopoulos, P. Heretsch, D. Gigue�re,

Y.-P. Sun, D. Sarlah, T. H. Nguyen, I. C. Wolf, D. F. Smee, C. W.Day, S. Bopp, E. A. Winzeler, J. Am. Chem. Soc. 2012, 134, 17320.

[23] I. D. Ivanchikova, N. I. Lebedeva, M. S. Shvartsberg, Synthesis 2004,2131.

[24] T. Kashiki, S. Shinamura, M. Kohara, E. Miyazaki, K. Takimiya, M.Ikeda, H. Kuwabara, Org. Lett. 2009, 11, 2473.

[25] D. Ma, S. Xie, P. Xue, X. Zhang, J. Dong, Y. Jiang, Angew. Chem.2009, 121, 4286; Angew. Chem. Int. Ed. 2009, 48, 4222.

[26] C. Li, X. Zhang, R. Tang, P. Zhong, J. Li, J. Org. Chem. 2010, 75,7037.

[27] N. Azizi, E. Akbari, F. Ebrahimi, M. R. Saidi, Monatsh. Chem. 2010,141, 323.

[28] W. You, X. Yan, Q. Liao, C. Xi, Org. Lett. 2010, 12, 3930.[29] H. Alper, F. Sibtain, J. Org. Chem. 1988, 53, 3306.[30] E. Iwasa, Y. Hamashima, S. Fujishiro, E. Higuchi, A. Ito, M. Yoshi-

da, M. Sodeoka, J. Am. Chem. Soc. 2010, 132, 4078.[31] J. E. DeLorbe, S. Y. Jabri, S. M. Mennen, L. E. Overman, F.-L.

Zhang, J. Am. Chem. Soc. 2011, 133, 6549.[32] S. Y. Jabri, L. E. Overman, J. Am. Chem. Soc. 2013, 135, 4231.[33] J. Kim, J. A. Ashenhurst, M. Movassaghi, Science 2009, 324, 238.[34] L. E. Overman, T. Sato, Org. Lett. 2007, 9, 5267.[35] J. Kim, M, Movassaghi, J. Am. Chem. Soc. 2010, 132, 14376.[36] D. J. Jansen, R. A. Shenvi, J. Am. Chem. Soc. 2013, 135, 1209.[37] a) C. Lai, B. J. Backes, Tetrahedron Lett. 2007, 48, 3033; b) A. van

den Hoogenband, J. W. Lange, R. P. Bronger, A. R. Stoit, S. W. Tup-stra, Tetrahedron Lett. 2010, 51, 6877.

[38] N. Park, K. Park, M. Jang, S. Lee, J. Org. Chem. 2011, 76, 4371.[39] K. M. Wager, M. H. Daniels, Org. Lett. 2011, 13, 4052.[40] F. Ke, Y. Qu, Z. Jiang, Z. Li, D. Wu, X. Zhou, Org. Lett. 2011, 13,

454.[41] F. Wang, C. Chen, G. Deng, C. Xi, J. Org. Chem. 2012, 77, 4148.[42] C. Savarin, J. Srogl, L. S. Liebeskind, Org. Lett. 2002, 4, 4309.[43] H. Wang, D. Huang, D. Cheng, L. Li, Y. Shi, Org. Lett. 2011, 13,

1650.[44] a) H. Tohma, Y. Harayama, M. Hashizume, M. Iwata, Y. Kiyono, M.

Egi, Y. Kita, J. Am. Chem. Soc. 2003, 125, 11235; b) H. Tohma, Y.Harayama, M. Hashizume, M. Iwata, M. Egi, Y. Kita, Angew. Chem.2002, 114, 358; Angew. Chem. Int. Ed. 2002, 41, 348.

[45] a) A. M. Rane, E. I. Miranda, J. A. Soderquist, Tetrahedron Lett.1994, 35, 3225; b) J. C. Arnould, M. Didelot, C. Cadilhac, M. J. Pas-quet, Tetrahedron Lett. 1996, 37, 4523; c) M. S. Harr, A. L. Presley,A. Thorarensen, Synlett 1999, 1579; d) M. Kreis, S. Br�se, Adv.Synth. Catal. 2005, 347, 313.

[46] Y. Gareau, A. Orellana, Synlett 1997, 803.[47] Y. Gareau, J. Pellicelli, S. Laliberte, D. Gauvreau, Tetrahedron Lett.

2003, 44, 7821.[48] V. Guilarte, M. A. Fern�ndez-Rodr�guez, P. Garc�a-Garc�a, E. Her-

nando, R. Sanz, Org. Lett. 2011, 13, 5100.[49] D. J. C. Prasad, G. Sekar, Org. Lett. 2011, 13, 1008.[50] V. K. Akkilagunta, R. R. Kakulapati, J. Org. Chem. 2011, 76, 6819.[51] Y. Liu, W. Bao, Tetrahedron Lett. 2007, 48, 4785.[52] C. Zhou, C. Fu, S. Ma, Angew. Chem. 2007, 119, 4457; Angew.

Chem. Int. Ed. 2007, 46, 4379.[53] Z. Qiao, H. Liu, X. Xiao, Y. Fu, J. Wei, Y. Li, X. Jiang, Org. Lett.

2013, 15, 2594.[54] H. Han, W. Zhao, J. Song, C. Li, H. Wang, J. Org. Chem. 2013, 78,

2726.[55] G. Teverovskiy, D. S. Surry, S. L. Buchwald, Angew. Chem. 2011,

123, 7450; Angew. Chem. Int. Ed. 2011, 50, 7312.[56] C.-P. Zhang, D. A. Vicic, J. Am. Chem. Soc. 2012, 134, 183.[57] J. Liu, L. Chu, F.-L. Qing, Org. Lett. 2013, 15, 894.[58] L. D. Tran, I. Popov, O. Daugulis, J. Am. Chem. Soc. 2012, 134,

18237.[59] a) J. M. Baskin, Z. Wang, Org. Lett. 2002, 4, 4423; b) J. M. Baskin,

Z. Wang, Tetrahedron Lett. 2002, 43, 8479.[60] W. Zhu, D. Ma, J. Org. Chem. 2005, 70, 2696.[61] a) M. Bian, F. Xu, C. Ma, Synthesis 2007, 19, 2951; b) W. Bao, C.

Wang, J. Chem. Res. 2006, 6, 396.[62] F.-L. Yang, S.-K. Tian, Angew. Chem. 2013, 125, 5029; Angew.

Chem. Int. Ed. 2013, 52, 4929.[63] W. Keim, J. Herwig, J. Chem. Soc. Chem. Commun. 1993, 1592.[64] a) K. Takagi, Chem. Lett. 1985, 1307; b) K. Takagi, Chem. Lett. 1986,

1379.[65] K. Takagi, Chem. Lett. 1986, 265.[66] H. Firouzabadi, N. Iranpoor, M. Gholinejad, Adv. Synth. Catal.

2010, 352, 119.[67] a) H. Firouzabadi, N. Iranpoor, M. Abbasi, Tetrahedron 2009, 65,

5293; b) T. Ramana, P. Saha, M. Das, T. Punniyamurthy, Org. Lett.2010, 12, 84; c) L. Chu, X. Yue, F. Qing, Org. Lett. 2010, 12, 1644.

[68] M. Kuhn, F. C. Falk, J. Paradies, Org. Lett. 2011, 13, 4100.[69] D. S. Baranov, B. Gold, S. F. Vasilevsky, I. V. Alabugin, J. Org.

Chem. 2013, 78, 2074.[70] Z. Yin, Y. Wang, Q. Yang, Y. Wang, J. Xu, Z. Deng, Y. Peng, Synthe-

sis 2013, 759.[71] Y. Ouyang, D. Dong, H. Yu, Y. Liang, Q. Liu, Adv. Synth. Catal.

2006, 348, 206.[72] A. Z. Halimehjani, M. H. Shayegan, M. M. Hashemi, B. Notash,

Org. Lett. 2012, 14, 3838.[73] M. Jana, A. K. Misra, J. Org. Chem. 2013, 78, 2680.[74] a) R. A. Cherkasov, G. A. Kutyrev, A. N. Pudovik, Tetrahedron

1985, 41, 2567; b) M. S. J. Foreman, J. D. Woollins, J. Chem. Soc.Dalton Trans. 2000, 1533; c) M. Jesberger, T. P. Davis, L. Barner,Synthesis 2003, 1929; d) M. P. Cava, M. I. Levinson, Tetrahedron1985, 41, 5061; e) B. S. Pedersen, S. Scheibye, N. H. Nilsson, S.-O.Lawesson, Bull. Soc. Chim. Belg. 1978, 87, 223.

[75] J. Bergman, B. Pettersson, V. Hasimbegovic, P. H. Svensson, J. Org.Chem. 2011, 76, 1546.

Received: May 6, 2013Published online: && &&, 0000




http://dx.doi.org/10.1021/ol302497mhttp://dx.doi.org/10.1002/chem.201103525http://dx.doi.org/10.1039/c3ob40464ahttp://dx.doi.org/10.1039/c3ob40464ahttp://dx.doi.org/10.1021/ol902186dhttp://dx.doi.org/10.1021/ol902186dhttp://dx.doi.org/10.1016/j.tetlet.2013.03.014http://dx.doi.org/10.1055/s-0032-1316897http://dx.doi.org/10.1021/ja2032635http://dx.doi.org/10.1021/ja209354ehttp://dx.doi.org/10.1021/ja209354ehttp://dx.doi.org/10.1021/ja308429fhttp://dx.doi.org/10.1021/ol900809whttp://dx.doi.org/10.1002/ange.200900486http://dx.doi.org/10.1002/ange.200900486http://dx.doi.org/10.1002/anie.200900486http://dx.doi.org/10.1021/jo101675fhttp://dx.doi.org/10.1021/jo101675fhttp://dx.doi.org/10.1007/s00706-010-0261-0http://dx.doi.org/10.1007/s00706-010-0261-0http://dx.doi.org/10.1021/ol101619shttp://dx.doi.org/10.1021/jo00249a031http://dx.doi.org/10.1021/ja101280phttp://dx.doi.org/10.1021/ja201789vhttp://dx.doi.org/10.1021/ja401423jhttp://dx.doi.org/10.1126/science.1170777http://dx.doi.org/10.1021/ol702518thttp://dx.doi.org/10.1021/ja106869shttp://dx.doi.org/10.1021/ja310778thttp://dx.doi.org/10.1016/j.tetlet.2007.02.128http://dx.doi.org/10.1016/j.tetlet.2010.10.125http://dx.doi.org/10.1021/jo2007253http://dx.doi.org/10.1021/ol201564jhttp://dx.doi.org/10.1021/ol102784chttp://dx.doi.org/10.1021/ol102784chttp://dx.doi.org/10.1021/jo300250xhttp://dx.doi.org/10.1021/ol026948ahttp://dx.doi.org/10.1021/ol200127nhttp://dx.doi.org/10.1021/ol200127nhttp://dx.doi.org/10.1021/ja0365330http://dx.doi.org/10.1002/1521-3757(20020118)114:2%3C358::AID-ANGE358%3E3.0.CO;2-2http://dx.doi.org/10.1002/1521-3757(20020118)114:2%3C358::AID-ANGE358%3E3.0.CO;2-2http://dx.doi.org/10.1002/1521-3773(20020118)41:2%3C348::AID-ANIE348%3E3.0.CO;2-Ihttp://dx.doi.org/10.1016/S0040-4039(00)76870-5http://dx.doi.org/10.1016/S0040-4039(00)76870-5http://dx.doi.org/10.1016/0040-4039(96)00873-8http://dx.doi.org/10.1055/s-1999-2910http://dx.doi.org/10.1002/adsc.200404299http://dx.doi.org/10.1002/adsc.200404299http://dx.doi.org/10.1055/s-1997-5774http://dx.doi.org/10.1016/j.tetlet.2003.08.073http://dx.doi.org/10.1016/j.tetlet.2003.08.073http://dx.doi.org/10.1021/ol201970mhttp://dx.doi.org/10.1021/ol103041shttp://dx.doi.org/10.1021/jo200793khttp://dx.doi.org/10.1016/j.tetlet.2007.03.168http://dx.doi.org/10.1002/ange.200700619http://dx.doi.org/10.1002/anie.200700619http://dx.doi.org/10.1002/anie.200700619http://dx.doi.org/10.1021/ol400618khttp://dx.doi.org/10.1021/ol400618khttp://dx.doi.org/10.1021/jo302635yhttp://dx.doi.org/10.1021/jo302635yhttp://dx.doi.org/10.1002/ange.201102543http://dx.doi.org/10.1002/ange.201102543http://dx.doi.org/10.1002/anie.201102543http://dx.doi.org/10.1021/ja210364rhttp://dx.doi.org/10.1021/ol400032ghttp://dx.doi.org/10.1021/ja3092278http://dx.doi.org/10.1021/ja3092278http://dx.doi.org/10.1021/ol0269190http://dx.doi.org/10.1016/S0040-4039(02)02073-7http://dx.doi.org/10.1021/jo047758bhttp://dx.doi.org/10.1002/ange.201301437http://dx.doi.org/10.1002/anie.201301437http://dx.doi.org/10.1002/anie.201301437http://dx.doi.org/10.1039/c39930001592http://dx.doi.org/10.1246/cl.1985.1307http://dx.doi.org/10.1246/cl.1986.1379http://dx.doi.org/10.1246/cl.1986.1379http://dx.doi.org/10.1246/cl.1986.265http://dx.doi.org/10.1002/adsc.200900671http://dx.doi.org/10.1002/adsc.200900671http://dx.doi.org/10.1016/j.tet.2009.04.079http://dx.doi.org/10.1016/j.tet.2009.04.079http://dx.doi.org/10.1021/ol9024088http://dx.doi.org/10.1021/ol9024088http://dx.doi.org/10.1021/ol100449chttp://dx.doi.org/10.1021/ol2016093http://dx.doi.org/10.1021/jo302146rhttp://dx.doi.org/10.1021/jo302146rhttp://dx.doi.org/10.1002/adsc.200505331http://dx.doi.org/10.1002/adsc.200505331http://dx.doi.org/10.1021/jo302115khttp://dx.doi.org/10.1016/S0040-4020(01)96363-Xhttp://dx.doi.org/10.1016/S0040-4020(01)96363-Xhttp://dx.doi.org/10.1055/s-2003-41447http://dx.doi.org/10.1016/S0040-4020(01)96753-5http://dx.doi.org/10.1016/S0040-4020(01)96753-5http://dx.doi.org/10.1021/jo101865yhttp://dx.doi.org/10.1021/jo101865y

本文献由“学霸图书馆-文献云下载”收集自网络，仅供学习交流使用。

学霸图书馆（www.xuebalib.com）是一个“整合众多图书馆数据库资源，

提供一站式文献检索和下载服务”的24 小时在线不限IP

图书馆。

图书馆致力于便利、促进学习与科研，提供最强文献下载服务。

图书馆导航：

图书馆首页文献云下载图书馆入口外文数据库大全疑难文献辅助工具

http://www.xuebalib.com/cloud/http://www.xuebalib.com/http://www.xuebalib.com/cloud/http://www.xuebalib.com/http://www.xuebalib.com/vip.htmlhttp://www.xuebalib.com/db.phphttp://www.xuebalib.com/zixun/2014-08-15/44.htmlhttp://www.xuebalib.com/

Transfer of sulfur: from simple to diverse.学霸图书馆link:学霸图书馆

transfer of sulfur: from simple to diverse.download.xuebalib.com/3sismsp8nxcn.pdf · doi:...

Documents