Recent Advances in Transition-Metal-Catalyzed C—S Bond Activation and Transformations

doi:10.6023/cjoc202309012

Abstract

The activation of C—S bond plays a crucial role in the preparation of drug molecules, high-performance polymers and composite materials, as well as in biomedical, environmental protection and other fields. Transition-metal-catalyzed C—S bond activation and transformations have a wide range of application prospects. Herein, the recent advances in transition-metal-catalyzed C(sp)/C(sp²)/C(sp³)—S bond activation and transformations are summarized according to the hybridization types of carbon atoms in organosulfur compounds. Various transition metal catalysts are utilized. The substrate applicability and reaction mechanisms are emphatically discussed. Finally, the challenges and future development trends of this research field are discussed and prospected.

Key words: C—S bond activation, transition metal catalysis, organosulfur compounds

Cite this article

Kaijie Guo, Xinshu Fu, Jing Li, Yan Chen, Meili Hu, Xihua Du, Yuyang Xie, Yan He. Recent Advances in Transition-Metal-Catalyzed C—S Bond Activation and Transformations[J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1124-1150.

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Fig. & Tab. 38

Figure 1. C—S bond cleavage strategies

Figure 2. Modeling of transition-metal-catalyzed C—S bond activation reaction

Scheme 1. Transition metal rhodium-catalyzed alkynyl sulfides and terminal alkynes for the synthesis of alkenyl sulfides

Scheme 2. Transition metal palladium-catalyzed cyclization of β-alkylthio derivatives for the synthesis of 2-cyclopentenones

Scheme 3. Transition metal palladium-catalyzed the cross-coupling of (2-methylthio-3-ester)benzofurans with 2-hydroxyphenylboronic acids and sequential intramolecular transesterification process

Scheme 4. Transition metal palladium-catalyzed cyclization of benzyne and enone dithioacetal

Scheme 5. Transition metal palladium-catalyzed the cross-coupling of aryl sulfides with arylzinc reagents

Scheme 6. Transition metal palladium-catalyzed the cross- coupling of arylsulfonium salt and sodium tetrarylborates

Scheme 7. Transition metal palladium-catalyzed desulfurative carbocyclizations reaction of α-(3-butenoyl) ketene dithioacetals

Scheme 8. α-Acyl ketene dithioacetals and isocyanides for the synthesis of 5-hydroxy-α,β-unsaturated γ-lactams

Scheme 9. Transition metal palladium-catalyzed arylation of arylboronic acids with Yagupolskii-Umemoto reagents

Scheme 10. Transition metal palladium-catalyzed carbothiolation of terminal alkynes and azolyl sulfides

Scheme 11. Transition metal palladium-catalyzed the [4+1] annulation of tetrasubstituted α-oxo ketene dithioacetals and allenoates

Scheme 12. Transition metal palladium-catalyzed the carbonylation of tert-butyl isocyanides into the C(sp2)—S bonds of heteroaryl sulfides

Scheme 13. Transition metal palladium-catalyzed alkoxycarbonylation of aryldimethylsulfoniums

Scheme 14. Transition metal palladium-catalyzed carbothiolation of terminal alkynes with heteroaryl sulfides

Scheme 15. Transition metal palladium-catalyzed carbonylative C—S bond activation of divinyl sulfides

Scheme 16. Tr ansition metal palladium catalyzes the intramolecular cyclization of alkenes

Scheme 17. Transition metal palladium-catalyzed Buchwald-Hartwig amination and C—S metathesis of aryl sulfides

Scheme 18. Transition metal nickel-catalyzed the cross-coupling of sulfur-functionalities and Grignard reagents

Scheme 19. Transition metal nickel-catalyzed Negishi-type cross-coupling of aryl methyl sulfoxides and arylzinc reagents

Scheme 20. Transition metal nickel-catalyzed aryldimethylsulfonium triflates and zinc powder for the synthesis of salt-free arylzinc triflates

Scheme 21. Transition metal nickel-catalyzed alkyne and 2-(trifluoromethyl)-1,3-benzothiazole for the synthesis of 2-(trifluoromethyl)- quinoline

Scheme 22. Transition metal nickel-catalyzed non-activated C(sp2)—S bond cleavage for the synthesis of sulfur-containing polycyclic compounds

Scheme 23. Transition metal nickel-catalyzed carbonylation of aryl iodides and thioacetates for the synthesis of thioesters

Scheme 24. Transition metal rhodium-catalyzed the cross-coupling of aryl methyl thioether derivatives and aryl boroxines

Scheme 25. Transition metal rhodium-catalyzed ipso-borylation of alkyl aryl sulfides via C(sp2)—S bond cleavage

Scheme 26. Transition metal iron-catalyzed α-oxo ketene dithioacetals with β-ketoesters and analogues for the synthesis of tetrasubstituted furans

Scheme 27. Transition metal iron-catalyzed sulfides for the synthesis of arylsilanes

Scheme 28. Transition metal copper/L-proline-catalyzed 2-(2-bromophenyl)-4,5-diaryl-1H-imidazole with potassium ethylxanthate for the synthesis of bis(2-(4,5-diaryl-1H-imidazol-2-yl)phenyl)sulfane derivatives

Scheme 29. Transition metal palladium/copper-catalyzed Sonogashira cross-coupling of terminal alkynes with arylsulfonium salts

Scheme 30. Transition metal palladium-catalyzed sequential catalytic arylations of sulfone compounds

Scheme 31. Transition metal palladium-catalyzed direct ortho alkylation of aromatic amide derivatives and alkyl dibenzothiophenium salts

Scheme 32. Transition metal palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters

Scheme 33. Transition metal palladium-catalyzed direct carbonylative thiomethylation of aryldiazonium salts or aromatic amines with 4-methylthio-2-butanone

Scheme 34. Transition metal iron-catalyzed tandem Friedel-Crafts alkylation-hydrolysis reaction of chain α-oxo ketene dithioacetals with alcohols

Scheme 35. Transition metal rhodium-catalyzed cross-coupling of benzyl thioethers and aryl carboxylic acids

Scheme 36. Transition metal palladium/copper-catalyzed Sono- gashira cross-coupling of terminal alkynes with (2-bromoethyl)- diphenylsulfonium triflate

References 53

[1]	(a) Wächtershäuser G. Trans. R. Soc. B 2006, 361, 1787. doi: 10.1098/rstb.2006.1904 pmid: 20704269
	(b) Harpp D. N.; Vines S. M.; Montillier J. P.; Chan T. H. J. Org. Chem. 1976, 41, 3987. doi: 10.1021/jo00887a012 pmid: 20704269
	(c) Grochowski M. R.; Li T.; Brennessel W. W.; Jones W. D. J. Am. Chem. Soc. 2010, 132, 12412. doi: 10.1021/ja104158h pmid: 20704269
[2]	(a) Boyd D. A. Angew. Chem., Int. Ed. 2016, 55, 15486. doi: 10.1002/anie.v55.50
	(b) Liu J.; Yang J.; Yang Q.; Wang G.; Li Y. Adv. Funct. Mater. 2005, 15, 1297. doi: 10.1002/(ISSN)1616-3028
	(c) Dondoni A. Angew. Chem., Int. Ed. 2008, 120, 9133. doi: 10.1002/ange.v120:47
[3]	(a) Natarajan A.; Guo Y.; Harbinski F.; Fan Y.-H.; Chen H.; Luus L.; Diercks J.; Aktas H.; Chorev M.; Halperin J. A. J. Med. Chem. 2004, 47, 4979. pmid: 19588965
	(b) Cole D. C.; Lennox W. J.; Lombardi S.; Ellingboe J. W.; Bernotas R. C.; Tawa G. J.; Mazandarani H.; Smith D. L.; Zhang G.; Coupet J.; Schechter L. E. J. Med. Chem. 2005, 48, 353. doi: 10.1021/jm049243i pmid: 19588965
	(c) Banerjee M.; Poddar A.; Mitra G.; Surolia A.; Owa T.; Bhattacharyya B. J. Med. Chem. 2005, 48, 547. pmid: 19588965
	(d) Feng E.; Huang H.; Zhou Y.; Ye D.; Jiang H.; Liu H. J. Comb. Chem. 2010, 12, 422. doi: 10.1021/cc9001839 pmid: 19588965
	(e) Gao G.-Y.; Colvin A. J.; Chen Y.; Zhang X. P. J. Org. Chem. 2004, 69, 8886. doi: 10.1021/jo048552d pmid: 19588965
	(f) Inamoto K.; Hasegawa C.; Hiroya K.; Doi T. Org. Lett. 2008, 10, 5147. doi: 10.1021/ol802033p pmid: 19588965
	(g) Jegelka M.; Plietker B. Org. Lett. 2009, 11, 3462. doi: 10.1021/ol901297s pmid: 19588965
	(h) Niu P.; Kang J.; Tian X.; Song L.; Liu H.; Wu J.; Yu W.; Chang J. J. Org. Chem. 2015, 80, 1018. doi: 10.1021/jo502518c pmid: 19588965
[4]	(a) Fang R.; Xu J.; Wang D.-W. Energy Environ. Sci. 2020, 13, 432. doi: 10.1039/C9EE03408K
	(b) Shi F.; Yu J.; Chen C.; Lau S. P.; Lv W.; Xu Z.-L. J. Mater. Chem. A 2022, 10, 19412. doi: 10.1039/D2TA02217F
	(c) Li M.; Chen H.; Wang Y.; Chen X.; Wu J.; Su J.; Wang M.; Li X.; Li C.; Ma L.; Li X.; Chen Y. J. Mater. Chem. A 2023, 11, 11721. doi: 10.1039/D3TA01803B
[5]	(a) Luque R. Curr. Org. Synth. 2011, 8, 1. doi: 10.2174/157017911794407665
	(b) Ornellas S. D.; Storr T. E.; Williams T. J.; Baumann C. G.; Fairlamb I. J. S. Curr. Org. Synth. 2011, 8, 79. doi: 10.2174/157017911794407656
	(c) Wang L.; He W.; Yu Z. Chem. Soc. Rev. 2013, 42, 599. doi: 10.1039/C2CS35323G
	(d) Modha S. G.; Mehta V. P.; Eycken E. V. Chem. Soc. Rev. 2013, 42, 5042. doi: 10.1039/c3cs60041f
	(e) Lou J.; Wang Q.; Wu P.; Wang H.; Zhou Y. G.; Yu Z. Chem. Soc. Rev. 2020, 49, 4307. doi: 10.1039/C9CS00837C
	(f) Huang S.; Wang M.; Jiang X. Chem. Soc. Rev. 2022, 51, 8351. doi: 10.1039/D2CS00553K
	(g) Otsuka S.; Nogi K.; Yorimitsu H. Top. Curr. Chem. 2018, 376, 13.
[6]	(a) Li Y.; Wang H.; Wang Z.; Alhumade H.; Huang Z.; Lei A. Chem. Sci. 2023, 14, 372. doi: 10.1039/D2SC05507D
	(b) Tyagi A.; Taneja N.; Khan J.; Hazra C. K. Adv. Synth. Catal. 2023, 365, 1247. doi: 10.1002/adsc.v365.8
	(c) Liang D.; Wang M.; Bekturhun B.; Xiong B.; Liu Q. Adv. Synth. Catal. 2010, 352, 1593. doi: 10.1002/adsc.v352:10
	(d) Liu Y.; Wang M.; Yuan H.; Liu Q. Adv. Synth. Catal. 2010, 352, 884. doi: 10.1002/adsc.v352:5
	(e) Liu Y.; Liu J.; Wang M.; Liu J.; Liu Q. Adv. Synth. Catal. 2012, 354, 2678. doi: 10.1002/adsc.v354.14/15
	(f) Yu H.; Yu Z. Angew. Chem. 2009, 121, 2973. doi: 10.1002/ange.v121:16
	(g) Dong Y.; Wang M.; Liu J.; Ma W.; Liu Q. Chem. Commun. 2011, 47, 7380. doi: 10.1039/c1cc11382h
	(h) Verma R. K.; Verma G. K.; Shukla G.; Singh M. S. RSC Adv. 2012, 2, 2413. doi: 10.1039/c2ra00987k
	(i) Jin W.; Du W.; Yang Q.; Yu H.; Chen J.; Yu Z. Org. Lett. 2011, 13, 4272. doi: 10.1021/ol201620g
[7]	Yang K.; Li Q.; Li Z.; Sun X. Chem. Commun. 2023, 59, 5343. doi: 10.1039/D3CC00377A
[8]	Liebeskind L. S.; Srogl J.; Savarin C.; Polanco C. Pure Appl. Chem. 2002, 74, 115. doi: 10.1351/pac200274010115
[9]	Iwasaki M.; Fujino D.; Wada T.; Kondoh A.; Yorimitsu H.; Oshima K. Chem. Asian J. 2011, 6, 3190. doi: 10.1002/asia.v6.12
[10]	Arisawa M.; Igarashi Y.; Tagami Y.; Yamaguchi M.; Kabuto C. Tetrahedron Lett. 2011, 52, 920 doi: 10.1016/j.tetlet.2010.12.065
[11]	Shibata T.; Mitake A.; Akiyamac Y.; Stephen K. K. Chem. Commun. 2017, 53, 9016. doi: 10.1039/C7CC04997H
[12]	Beletskaya I. P.; Ananikov V. P. Chem. Rev. 2022, 122, 16110. doi: 10.1021/acs.chemrev.1c00836 pmid: 36112510
[13]	(a) Beletskaya I. P.; Alonso F.; Tyurin V. Coord Chem. Rev. 2019, 385, 137. doi: 10.1016/j.ccr.2019.01.012
	(b) Buchspies J.; Szostak M. Catalysts 2019, 9, 53. doi: 10.3390/catal9010053
	(c) Das P.; Linert W. Coord. Chem. Rev. 2016, 311, 1. doi: 10.1016/j.ccr.2015.11.010
	(d) Han F.-S. Chem. Soc. Rev. 2013, 42, 5270. doi: 10.1039/c3cs35521g
	(e) Hooshmand S. E.; Heidari B.; Sedghi R.; Varma R. S. Green chem. 2019, 21, 381. doi: 10.1039/c8gc02860e
	(f) Lennox A. J. J.; Lloyd-Jones G. C. Chem. Soc. Rev. 2014, 43, 412. doi: 10.1039/C3CS60197H
	(g) Lamblin M.; Nassar-Hardy L.; Hierso J.-C.; Fouquet E.; Felpin F.-X. Adv. Synth. Catal. 2010, 352, 33. doi: 10.1002/adsc.v352:1
[14]	Liu B.; Zheng G.; Liu X.; Xu C.; Liu J.; Wang M. Chem. Commun. 2013, 49, 2201. doi: 10.1039/c3cc37571d
[15]	Liu J.; Liu Y.; Du W.; Dong Y.; Liu J.; Wang M. J. Org. Chem. 2013, 78, 7293. doi: 10.1021/jo400984h
[16]	Dong Y.; Liu B.; Chen P.; Liu Q.; Wang M. Angew. Chem. 2014, 126, 3510. doi: 10.1002/ange.v126.13
[17]	Otsuka S.; Fujino D.; Murakami K.; Yorimitsu H.; Osuka A. Chem. Eur. J. 2014, 20, 13146. doi: 10.1002/chem.v20.41
[18]	Vasu D.; Yorimitsu H.; Osuka A. Synthesis 2015, 47, 3286. doi: 10.1055/s-00000084
[19]	Liu B.; Chang J.; Zheng G.; Song X.; Wang M. Eur. J. Org. Chem. 2015, 4611.
[20]	Chang J.; Liu B.; Yang Y.; Wang M. Org. Lett. 2016, 18, 3984. doi: 10.1021/acs.orglett.6b01780 pmid: 27498923
[21]	Wang S.-M.; Wang X.-Y.; Qin H.-L.; Zhang C.-P. Chem. Eur. J. 2016, 22, 6542. doi: 10.1002/chem.v22.19
[22]	Iwasaki M.; Topolovčan N.; Hu H.; Nishimura Y.; Gagnot G.; Na nakorn R.; Yuvacharaskul R.; Nakajima K.; Nishihara Y. Org. Lett. 2016, 18, 1642. doi: 10.1021/acs.orglett.6b00503
[23]	Wang Q.; Liu Z.; Lou J.; Yu Z. Org. Lett. 2018, 20, 6007. doi: 10.1021/acs.orglett.8b02253
[24]	Otsuka S.; Nogi K.; Yorimitsu H. Angew. Chem., Int. Ed. 2018, 57, 6653. doi: 10.1002/anie.v57.22
[25]	Minami H.; Nogi K.; Yorimitsu H. Org. Lett. 2019, 21, 2518. doi: 10.1021/acs.orglett.9b00067
[26]	Uno D.; Nogi K.; Yorimitsu H. Org. Lett. 2019, 21, 8295. doi: 10.1021/acs.orglett.9b03056
[27]	Xu J.-X.; Zhao F.; Wu X.-F. Org. Biomol. Chem. 2020, 18, 9796. doi: 10.1039/D0OB02043E
[28]	Delcaillau T.; Schmitt H. L.; Boehm P.; Falk E.; Morandi B. ACS Catal. 2022, 12, 6081. doi: 10.1021/acscatal.2c01178
[29]	Yang S.; Yu X.; Poater A.; Cavallo L.; Cazin C. S. J.; Nolan S. P.; Szostak M. Org. Lett. 2022, 24, 9210. doi: 10.1021/acs.orglett.2c03717
[30]	Mond J.; Langer C.; Quincke F. J. Chem. Soc., Trans. 1890, 57, 749. doi: 10.1039/CT8905700749
[31]	Wilke G. Angew. Chem., Int. Ed. 1988, 27, 185.
[32]	Stephan Enthaler, C. I. S. M. W. Catal. Lett. 2013, 143, 424. doi: 10.1007/s10562-013-0979-5
[33]	Yamamoto K.; Otsuka S.; Nogi K.; Yorimitsu H. ACS Catal. 2017, 7, 7623. doi: 10.1021/acscatal.7b02347
[34]	Yamada K.; Yanagi T.; Yorimitsu H. Org. Lett. 2020, 22, 9712. doi: 10.1021/acs.orglett.0c03782 pmid: 33300805
[35]	Inami T.; Kurahashi T.; Matsubara S. Synlett 2021, 32, 1948. doi: 10.1055/s-0037-1610785
[36]	Shibata T.; Sekine A.; Akino M.; Ito M. Chem. Commun., 2021, 57, 9048. doi: 10.1039/D1CC03226G
[37]	Mai W.-P.; Sui H.-D.; Lv M.-X.; Lu K. J. Chem. Res. 2021, 45, 890. doi: 10.1177/17475198211028114
[38]	Pan F.; Wang H.; Shen P.-X.; Zhao J.; Shi Z.-J. Chem. Sci. 2013, 4, 1573. doi: 10.1039/c3sc22242j
[39]	Uetake Y.; Niwa T.; Hosoya T. Org. Lett. 2016, 18, 2758. doi: 10.1021/acs.orglett.6b01250 pmid: 27210907
[40]	(a) Sherry B. D.; Fürstner A. Acc. Chem. Res. 2008, 41, 1500. doi: 10.1021/ar800039x
	(b) Czaplik W. M.; Mayer M.; Cvengros, Wangelin, J.; A. Jacobi von. ChemSusChem 2009, 2, 396. doi: 10.1002/cssc.v2:5
	(c) Piontek A.; Bisz E.; Szostak M. Angew. Chem., Int. Ed. 2018, 57, 11116. doi: 10.1002/anie.v57.35
[41]	Blanksby S. J.; Ellison G. B. Acc. Chem. Res. 2003, 36, 255. doi: 10.1021/ar020230d
[42]	Lou J.; Wang Q.; Wu K.; Wu P.; Yu Z. Org. Lett. 2017, 19, 3287. doi: 10.1021/acs.orglett.7b01431
[43]	Chen S.; Guo X.; Hou H.; Geng S.; Liu Z.; He Y.; Xue X.-S.; Feng Z. Angew. Chem., Int. Ed. 2023, 62, e202303470. doi: 10.1002/anie.v62.25
[44]	Zhang Y.; Li T.-J.; Lv L.; Liu J.-Q.; Wang X.-S. J. Heterocyclic. Chem. 2022, 59, 67. doi: 10.1002/jhet.v59.1
[45]	Tian Z.-Y.; Wang S.-M.; Jia S.-J.; Song H.-X.; Zhang C.-P. Org. Lett. 2017, 19, 5454. doi: 10.1021/acs.orglett.7b02764
[46]	Li Y.; Wang H.; Wang Z.; Alhumade H.; Huang Z.; Lei A. Chem. Sci. 2023, 14, 372. doi: 10.1039/D2SC05507D
[47]	Nambo M.; Crudden C. M. Angew. Chem., Int. Ed. 2014, 53, 742. doi: 10.1002/anie.v53.3
[48]	Simkó D. C.; Elekes P.; Pázmándi V.; Novák Z. Org. Lett. 2018, 20, 676. doi: 10.1021/acs.orglett.7b03813
[49]	Li Y.; Bao G.; Wu X.-F. Chem. Sci. 2020, 11, 2187. doi: 10.1039/C9SC05532K
[50]	Tian Q.; Xu S.; Zhang C.; Liu X.; Wu X.; Li Y. J.Org. Chem. 2021, 86, 8797. doi: 10.1021/acs.joc.1c00665
[51]	Yu H.; Zhao L.; Diao Q.; Li T.; Liao P.; Hou D.; Xin G. Synlett 2017, 28, 1828. doi: 10.1055/s-0036-1588982
[52]	Zhang X.-S.; Zhang Y.-F.; Li Z.-W.; Luo F.-X.; Shi Z.-J. Angew. Chem., Int. Ed. 2015, 54, 5478. doi: 10.1002/anie.v54.18
[53]	Ming X.-X.; Wu S.; Tian Z.-Y.; Song J.-W.; Zhang C.-P. Org. Lett. 2021, 23, 6795. doi: 10.1021/acs.orglett.1c02379

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