Research Progress in Transition Metal⁃Catalyzed C-S Bond Cleavage of Organic Sulfides

doi:10.12422/j.issn.1006-396X.2023.01.007

Abstract

Abstract:

Organic sulfides widely exist in natural resources such as petroleum and coal,which have abundant resource reserves.In the petroleum refining industry,the cleavage of C-S bonds is usually required for the desulfurization of petroleum fractions. Among them,the transition metal?catalyzed cleavage reactions of C-S bonds have attracted the attention of researchers owing to the advantages of high efficiency,mild conditions,and low pollution.This review summarizes the progress in transition metal?catalyzed C-S bond cleavage reactions of different types of organic sulfides,and provides insights into Pd,Cu,Ni and Fe catalytic systems and mechanisms.Moreover,the development of such reactions is proposed.

Key words: Cross?coupling reaction, Transition metal catalysis, C-S bond, Organic sulfides, Research progress

摘要：

有机硫化物广泛存在于石油、煤炭等自然资源中，具有丰富的资源储备。在石油炼制工业中，通常需要通过C-S断裂进行石油馏分的脱硫。其中，过渡金属催化的C-S断裂反应因具有效率高、条件温和、污染小等优点而备受研究者的关注。总结了过渡金属催化不同类型有机硫化物C-S断裂反应的最新进展，对Pd、Cu、Ni、Fe等催化体系的反应机理提出了见解，并对该类反应的发展前景进行了展望。

关键词: 交叉偶联反应, 过渡金属催化, C-S, 有机硫化物, 研究进展

CLC Number:

TQ31.2

Shuainan Tian, Ran Sun, Lei Li, He Wang. Research Progress in Transition Metal⁃Catalyzed C-S Bond Cleavage of Organic Sulfides[J]. Journal of Petrochemical Universities, 2023, 36(1): 48-57.

田帅男, 孙然, 李蕾, 王贺. 过渡金属催化有机硫化物C-S断裂反应的研究进展[J]. 石油化工高等学校学报, 2023, 36(1): 48-57.

Figures/Tables 21

Fig.1 “Liebeskind–Srogl” cross?coupling reaction

Fig.2 CuI/Ag2CO3?catalyzed C-S bond cleavage of thiolesters

Fig.3 Nickel?catalyzed decarbonylative thioetherification of thioesters

Fig.4 Ni(COD)2 catalyzed decarbonylation of α?ketothioesters

Fig.5 Pd(OAc)2 catalyzed intramolecular decarbonylation coupling of thioesters

Fig.6 Pd?catalyzed C-S bond cleavage of thioalkylindoles and thioalkylfurans

Fig.7 C-S bond cleavage of α-oxoketene dithioacetal

Fig.8 Rh catalyzed C-S bond cleavage of alkylthioarenes

Fig.9 Cu?catalyzed cyclization of the α-oxoketene dithioacetal with diazo compounds

Fig.10 Ni?catalyzed cyanation of aryl sulfide

Fig.11 Iron?catalyzed difluoromethylation of arylzinc reagents with difluoromethyl 2-pyridyl sulfone

Fig.12 Nickel?catalyzed C(sp3)?C(sp2) coupling between PT?sulfones and aryl zinc reagents

Fig.13 Desulfonylative amination of benzhydryl sulfones

Fig.14 Pd-NHC catalyzed cross-coupling reaction of diphenyl sulfoxide and boronic acid

Fig.15 Ni?catalyzed borylation of diaryl sulfoxides

Fig.16 Cross?coupling of aryl sulfinates with aryl halides

Fig.17 Cross?coupling of sodium pyridyl sulfinate with arylhalides

Fig.18 Desulfurization reaction of pyridone and arylsulfonyl chloride

Fig.19 C-S bond cleavage in aryl thiocyanates

Fig.20 Direct coupling of thioureas and aryl halides

Fig.21 Direct coupling of aryl sulfonium salts and aryl halides

References 54

1	Thalgaspitiya W R K，Kankanam K T，He J，et al.High surface area mesoporous tungsten oxide for fast，green oxidation of organosulfur compounds in crude oil［J］.Applied Materials Today，2020，19：100616.
2	Jacob C.A scent of therapy：Pharmacological implications of natural products containing redox⁃active sulfur atoms［J］.Natural Product Reports，2006，23（6）：851⁃863.
3	Devendar P，Yang G F.Sulfur⁃containing agrochemicals［J］.Topics in Current Chemistry，2017，375（6）：82.
4	Pillai S D，Shayanfar S.Electron beam technology and other irradiation technology applications in the food industry［J］.Topics in Current Chemistry，2017，375（1）：6.
5	Ilardi E A，Vitaku E，Njardarson J T.Data⁃mining for sulfur and fluorine：An evaluation of pharmaceuticals to reveal opportunities for drug design and discovery［J］.Journal of Medicinal Chemistry，2014，57（7）：2832⁃2842.
6	李翔，王安杰，柳广厦，等.芳香杂环含硫化合物C-S键断裂方式［J］.石油学报（石油加工），2017，33（6）：1039⁃1052.
	Li X，Wang A J，Liu G S，et al.Mechanisms of the cleavage of C-S bonds in polyaromatic sulfur⁃containing compounds［J］.Acta Petrolei Sinica （Petroleum Processing Section），2017，33（6）：1039⁃1052.
7	Ding S，Jiang S，Zhou Y，et al.Catalytic characteristics of active corner sites in CoMoS nanostructure hydrodesulfurization⁃A mechanism study based on DFT calculations［J］.Journal of Catalysis，2017，345：24⁃38.
8	Ganiyu S A，Ali S A，Alhooshani K.Improved dispersion and ultradeep activity of HDS catalyst by new synthesis approach［J］.ChemistrySelect，2019，4（1）：370⁃377.
9	Brunet S，Mey D，Pérot G，et al.On the hydrodesulfurization of FCC gasoline：A review［J］.Applied Catalysis A：General，2005，278（2）：143⁃172.
10	Wang H，Iglesia E.Thiophene hydrodesulfurization catalysis on supported Ru clusters：Mechanism and site requirements for hydrogenation and desulfurization pathways［J］.Journal of Catalysis，2010，273（2）：245⁃256.
11	孙丽娟，曹祖宾，韩冬云，等.过氧乙酸氧化⁃萃取脱除渣油中硫化合物［J］.辽宁石油化工大学学报，2021，41（3）：10⁃14.
	Sun L J，Cao Z B，Han D Y，et al.Removal of sulfur compounds in residue by peracetic acid oxidation⁃extraction［J］.Journal of Liaoning Petrochemical University，2021，41（3）：10⁃14.
12	商宇桐，杨丽娜，管景国，等.光催化氧化脱硫催化剂研究进展［J］.石油化工高等学校学报，2020，33（2）：17⁃22.
	Shang Y T，Yang L N，Guan J G，et al.Progress in photocatalytic oxidation desulfurization catalysts［J］.Journal of Petrochemical Universities，2020，33（2）：17⁃22.
13	Duan X G，Sun H Q，Shao Z P，et al.Nonradical reactions in environmental remediation processes：Uncertainty and challenges［J］.Applied Catalysis B：Environmental，2018，224：973⁃982.
14	Wang L，He W，Yu Z.Transition⁃metal mediated carbon⁃sulfur bond activation and transformations［J］.Chemical Society Reviews，2013，42（2）：599⁃621.
15	Nogi K，Yorimitsu H.Catalytic carbonylation and carboxylation of organosulfur compounds via C-S cleavage［J］.Chemistry an Asian Journal，2020，15（4）：441⁃449.
16	Jensen F，Greer A.Reaction of organic sulfides with singlet oxygen.A revised mechanism［J］.Journal of the American Chemical Society，1998，120（18）：4439⁃4449.
17	Clennan E L.Persulfoxide：Key intermediate in reactions of singlet oxygen with sulfides［J］.Accounts of Chemical Research，2001，34（11）：875⁃884.
18	Corey E J，Ouannes C.Intermédiaire dans l'oxydation de benzylalcoyl sulfures par l'oxygène singulet［J］.Tetrahedron Letters，1976，17（47）：4263⁃4266.
19	Zhang Y，Wang J.Alkene synthesis through transition metal⁃catalyzed cross⁃coupling of N⁃tosylhydrazones［J］.Topics in Current Chemistry，2012，327：1⁃32.
20	Surry D S，Buchwald S L.Dialkylbiaryl phosphines in Pd⁃catalyzed amination：A user's guide［J］.Chemical Science，2011，2（1）：27⁃50.
21	Srogl J，Allred G D，Liebeskind L S.Sulfonium salts.Participants par excellence in metal⁃catalyzed carbon⁃carbon bond⁃forming reactions［J］.Journal of the American Chemical Society，1997，119（50）：12376⁃12377.
22	Pan L，Bi X，Liu Q.Recent developments of ketene dithioacetal chemistry［J］.Chemical Society Reviews，2013，42（3）：1251⁃1286.
23	Modha S G，Mehta V P，Van Der Eycken E V.Transition metal⁃catalyzed C-C bond formation via C-S bond cleavage：An overview［J］.Chemical Society Reviews，2013，42（12）：5042⁃5055.
24	Zhu D，Shi L.Ni⁃catalyzed cross⁃coupling of aryl thioethers with alkyl Grignard reagents via C-S bond cleavage［J］.Chemical Communications，2018，54（67）：9313⁃9316.
25	Li Y，Rauchfuss T B.Synthesis of diiron（I） dithiolato carbonyl complexes［J］.Chemical Reviews，2016，116（12）：7043⁃7077.
26	Zhou Q，Zhang B，Du T，et al.Regioselective C-S bond formation accomplished by copper⁃catalyzed regioselective C-F substitution of perfluoroarenes with aryl thioacetates or benzyl thioacetate［J］.Tetrahedron，2012，68（22）：4233⁃4241.
27	Tang S Q，Bricard J，Schmitt M，et al.Fukuyama cross⁃coupling approach to isoprekinamycin：Discovery of the highly active and bench⁃stable palladium precatalyst POxAP［J］.Organic Letters，2019，21（3）：844⁃848.
28	Ren R，Wu Z.C-C bond⁃forming strategy by manganese⁃catalyzed oxidative ring⁃opening cyanation and ethynylation of cyclobutanol derivatives［J］.Angewandte Chemie⁃International Edition，2016，55（8）：2866⁃2869.
29	Naowarojna N，Cheng R，Chen L，et al.Mini⁃review：Ergothioneine and ovothiol biosyntheses，an unprecedented trans⁃sulfur strategy in natural product biosynthesis［J］.Biochemistry，2018，57（24）：3309⁃3325.
30	Ren P，Pike S D，Pernik I，et al.Rh⁃POP pincer xantphos complexes for C-S and C-H activation.Implications for carbothiolation catalysis［J］.Organometallics，2015，34（4）：711⁃723.
31	Iyori Y，Ueno R，Morishige A，et al.Nickel⁃catalyzed C-O/N-H，C-S/N-H，and C-CN/N-H annulation of aromatic amides with alkynes：C-O，C-S，and C-CN activation［J］.Chemical Science，2020，12（5）：1772⁃1777.
32	Liebeskind L S，Srogl J.Thiol ester⁃boronic acid coupling.A mechanistically unprecedented and general ketone synthesis［J］.Journal of the American Chemical Society，2000，122（45）：11260⁃11261.
33	Ghosh P，Ganguly B，Perl E，et al.A synthesis of biaryl ketones via the C-S bond cleavage of thiol ester by a Cu/Ag salt［J］.Tetrahedron Letters，2017，58（28）：2751⁃2756.
34	Lee S C，Liao H H，Chatupheeraphat A，et al.Nickel⁃catalyzed C-S bond formation via decarbonylative thioetherification of esters，amides and intramolecular recombination fragment coupling of thioesters［J］.Chemistry⁃A European Journal，2018，24（14）：3608⁃3612.
35	Zheng Z J，Jiang C，Shao P C，et al.Controlled Ni⁃catalyzed mono⁃ and double⁃decarbonylations of alpha⁃ketothioesters［J］.Chemical Communications，2019，55（13）：1907⁃1910.
36	Cao H，Liu X，Bie F，et al.General and practical intramolecular decarbonylative coupling of thioesters via palladium catalysis［J］.Organic Chemistry Frontiers，2021，8（7）：1587⁃1592.
37	Huang F，Wu P，Wang L，et al.Copper⁃mediated intramolecular oxidative C-H/C-H cross⁃coupling of alpha⁃oxo ketene N，S⁃acetals for indole synthesis［J］.The Journal of Organic Chemistry，2014，79（21）：10553⁃10560.
38	Lou J，Wang Q，Wu K，et al.Iron⁃catalyzed oxidative C-H functionalization of internal olefins for the synthesis of tetrasubstituted furans［J］.Organic Letters，2017，19（12）：3287⁃3290.
39	Guo T，Jiang Q，Yu Z.Copper⁃catalyzed ring⁃expansion/thiolactonizationviaazidation of internal olefinic C-H bond under mild conditions［J］.Advanced Synthesis & Catalysis，2016，358（21）：3450⁃3457.
40	Uetake Y，Niwa T，Hosoya T.Rhodium⁃catalyzed ipso⁃borylation of alkylthioarenes via C-S bond cleavage［J］.Organic Letters，2016，18（11）：2758⁃2761.
41	Sun R，Du Y，Tian C，et al.Copper（II）‐catalyzed domino reaction of the acyclic ketene‐（s，s）‐acetals with diazo compounds：Convenient synthesis of poly‐substituted thiophenes［J］.Advanced Synthesis & Catalysis，2019，361（24）：5684⁃5689.
42	He Y，Lou J，Wu P，et al.Copper⁃catalyzed annulative coupling of S，S⁃disubstituted enones with diazo compounds to access highly functionalized thiophene derivatives［J］.The Journal of Organic Chemistry，2020，85（2）：1044⁃1053.
43	Delcaillau T，Woenckhaus⁃Alvarez A，Morandi B.Nickel⁃catalyzed cyanation of aryl thioethers［J］.Organic Letters，2021，23（18）：7018⁃7022.
44	Miao W，Zhao Y，Ni C，et al.Iron⁃catalyzed difluoromethylation of arylzincs with difluoromethyl 2⁃pyridyl sulfone［J］.Journal of the American Chemical Society，2018，140（3）：880⁃883.
45	Merchant R R，Edwards J T.Modular radical cross⁃coupling with sulfones enables access to sp³⁃rich （fluoro） alkylated scaffolds［J］.Science，2018，360（6384）：75⁃80.
46	Nambo M，Tahara Y，Yim J C，et al.Cu⁃catalyzed desulfonylative amination of benzhydryl sulfones［J］.Chemistry⁃A European Journal，2019，25（8）：1923⁃1926.
47	Chen Q，Wu S，Yan S，et al.Suzuki–miyaura cross⁃coupling of sulfoxides［J］.ACS Catalysis，2020，10（15）：8168⁃8176.
48	Huang M，Wu Z，Krebs J，et al.Ni⁃catalyzed borylation of aryl sulfoxides［J］.Chemistry⁃A European Journal，2021，27（31）：8149⁃8158.
49	Gund S H，Balsane K E，Nagarkar J M.Palladium catalyzed desulfinylative couplings between aryl sulfinates and aryl bromide/iodide for the synthesis of biaryls［J］.Tetrahedron，2016，72（33）：5051⁃5056.
50	Markovic T，Rocke B N，Blakemore D C，et al.Pyridine sulfinates as general nucleophilic coupling partners in palladium⁃catalyzed cross⁃coupling reactions with aryl halides［J］.Chemical Science，2017，8（6）：4437⁃4442.
51	Karmakar U，Samanta R.A directing group free Pd（II）⁃catalysed desulfitative C₆⁃arylation of 2⁃pyridone using an arylsulfonyl chloride［J］.Organic & Biomolecular Chemistry，2020，18（40）：8079⁃8083.
52	Pawliczek M，Garve L K，Werz D B.Activation of aryl thiocyanates followed by aryne insertion：Access to 1，2⁃thiobenzonitriles［J］.Organic Letters，2015，17（7）：1716⁃1719.
53	Roy S，Phukan P.Biaryl thioether synthesis via CuI catalyzed dominothiolation of aryl halides in the presence of DMAP as ligand［J］.Tetrahedron Letters，2015，56（19）：2426⁃2429.
54	Ma N N，Ren J A，Liu X，et al.Nickel⁃catalyzed direct cross⁃coupling of aryl sulfonium salt with aryl bromide［J］.Organic Letters，2022，24（10）：1953⁃1957.