Ru-Mediated and Sulfur-Directed ortho-C–H Activation of Benzyl Thioethers with Internal Alkynes and Selective Hydrothiolation of Acetylene Dicarboxylates

Abstract

In this report, we have established a Ru(η⁶-C₆H₆)Cl₂ catalysed ortho-C–H activation of benzyl thioethers with alkynes under milder reaction conditions. The sulfur atom of benzyl thioethers worked as a directing group for ortho-C–H activation of benzyl thioethers. The reaction was found to tolerate a range of benzyl thioethers as well as alkynes. Moreover, the reaction is significantly influenced by the length of alkyl and aryl thioethers, with the best results being obtained with benzyl thioethers. Kinetic isotopic experiments suggest that the ortho-C–H bond-breaking is not a rate-determining step for the present reaction. In an unusual observation that has not been reported, apart from ortho-C–H activation, under the same reaction conditions, a selective debenzylative hydrothiolation was exclusively obtained with acrylates, which broadens the synthetic impact of benzyl thioethers for the preparation of mixed chalcogen ethers.

Key words

Ru-catalysis - sulfur directing groups - ortho-C–H activation - debenzylative hydrothiolation - thioethers

Publication History

Received: 11 April 2024

Accepted after revision: 19 June 2024

Accepted Manuscript online:
19 June 2024

Article published online:
22 July 2024

• References

• 1a Catellani M. Top. Organomet. Chem. 2005; 8: 21
• 1b Catellani M, Motti E, Ca ND. Acc. Chem. Res. 2008; 41: 1512
• 1c Jun C.-H, Moon CW, Lee D.-Y. Chem. Eur. J. 2002; 8: 2422
• 1d Park YJ, Jun C.-H. Bull. Korean Chem. Soc. 2005; 26: 877
• 1e Ackermann L, Vicente R. Top. Curr. Chem. 2009; 292: 211
• 2a Lewis LN, Smith JF. J. Am. Chem. Soc. 1986; 108: 2728
• 2b Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N. Nature 1993; 366: 529
• 3a Kim D.-S, Park J.-W, Jun C.-W. Adv. Synth. Catal. 2013; 355: 2667
• 3b Guimond N, Fagnou K. J. Am. Chem. Soc. 2009; 131: 12050
• 3c Wei X, Zhao M, Du Z, Li X. Org. Lett. 2011; 13: 4636
• 4a Miura M, Tsuda T, Satoh T, Pivsa-Art S, Nomura M. J. Org. Chem. 1998; 63: 5211
• 4b Ackermann J, Pospech L, Graczyk K, Rauch K. Org. Lett. 2012; 14: 930
• 5 Negi L, Soni A, Sharma C, Joshi RK. J. Organomet. Chem. 2023; 1001: 122847
• 6a Kumari S, Sharma C, Satrawala N, Srivastava AK, Sharma KN, Joshi RK. Organometallics 2022; 41: 1403
• 6b Kumari S, Sharma D, Sharma C, Negi L, Joshi RK. Org. Lett. 2024; 26: 1758
• 7 Kumari S, Sharma C, Srivastava AK, Satrawala N, Sharma KN, Joshi RK. Eur. J. Inorg. Chem. 2021; 3648
• 8a Naowarojna N, Cheng R, Chen L, Quill M, Xu M, Zhao C, Liu P. Biochemistry 2018; 57: 3309
• 8b Zhao J, Jiang X. Chin. Chem. Lett. 2018; 29: 1079
• 8c Tang KX, Wang CM, Gao TH, Chen L, Fan L, Sun LP. Adv. Synth. Catal. 2019; 361: 26
• 9 Ilardi EA, Vitaku E, Njardarson JT. J. Med. Chem. 2014; 57: 2832
• 10 McReynolds MD, Dougherty JM, Hanson PR. Chem. Rev. 2004; 104: 2239
• 11 Patai S, Rappoport Z. The Chemistry of Sulfur-Containing Functional Groups, Supplement S. Wiley; Chichester: 1993
• 12 Zhang J, Liu Y, Jia Q, Wang Y, Ma Y, Szostak M. Org. Lett. 2020; 22 (17) 6884
• 13 Jayakumar J, Cheng C.-H. J. Chin. Chem. Soc. 2018; 65: 11
• 14a Sharma C, Srivastava AK, Sharma KN, Joshi RK. Org. Biomol. Chem. 2020; 18: 3599
• 14b Sharma KN, Ali M, Srivastava AK, Joshi RK. J. Organomet. Chem. 2019; 879: 69
• 14c Sharma KN, Satrawala N, Joshi RK. Eur. J. Inorg. Chem. 2018; 1743
• 14d Tomar V, Sharma C, Nemiwal M, Joshi RK. J. Organomet. Chem. 2021; 956: 122095
• 14e Tomar V, Upadhyay Y, Srivastava AK, Nemiwal M, Joshi RK, Mathur P. J. Organomet. Chem. 2021; 940: 121752
• 14f Soni A, Sharma C, Negi LR. K. Joshi. J. Organomet. Chem. 2023; 983: 122550
• 14g Sharma C, Kumari S, Sharma D, Srivastava AK, Joshi RK. J. Org. Chem. 2024; 89: 701
• 15a Sharma C, Srivastava AK, Soni A, Kumari S, Joshi RK. RSC Adv. 2020, 10: 32516
• 15b Sharma D, Tomar V, Sharma C, Joshi RK. Tetrahedron 2022; 124: 133014
• 15c Sharma C, Srivastava AK, Sharma D, Joshi RK. New J. Chem. 2022; 46: 8551
• 16 Wang F, Wang W.-G, Wang X.-J, Wang H.-Y, Tung C.-H, Wu L, Wu L.-Z. Angew. Chem. Int. Ed. 2011; 50: 3193
• 17 Wang B, Liu Y, Lin C, Xu Y, Liu Z, Zhang Y. Org. Lett. 2014; 16 (17) 4574
• 18a Zhang XS, Zhu QL, Zhang YF, Li YB, Shi ZJ. Chem. Eur. J. 2013; 19 (36) 11898
• 18b Manikandana R, Jeganmohan M. Chem. Commun. 2017; 53: 8931
• 19a Unoh Y, Hirano K, Satoh T, Miura M. Org. Lett. 2015; 17 (03) 704
• 19b Manikandan R, Jeganmohan M. Org. Lett. 2014; 16: 912
• 20 Li C, Chen X, Bao R.-P, Li D.-L, Zhang K, Wang D.-H. RSC Adv. 2019; 9 (52) 30134
• 21 Villuendas P, Urriolabeitia EP. Org. Lett. 2015; 17: 3178
• 22a Rubin M, Trofimov A, Gevorgyan V. J. Am. Chem. Soc. 2005; 127 (29) 10243
• 22b Arcadi A, Aschi M, Chiarini M, Ferrara G, Marinelli F. Adv. Synth. Catal. 2010; 352: 493
• 22c Topolovčan N, Hara S, Císařová I, Tošner Z, Kotora M. Eur. J. Org. Chem. 2020; 234
• 23 Yu M, Xie Y, Xie C, Zhang Y. Org. Lett. 2012; 14: 2164
• 24 Jin XY, Xie LJ, Cheng HP, Liu AD, Li XD, Wang D, Cheng L, Liu L. J. Org. Chem. 2018; 83: 7514
• 25a Field L. Synthesis 1978; 713
• 25b Patai S, Rappoport Z, Stirling CJ. M. The Chemistry of Sulphones and Sulphoxides . Wiley; New York: 1988
• 26a Kupwade RV. J. Chem. Rev. 2019; 1: 99
• 26b Matavos-Aramyan S, Soukhakian S, Jazebizadeh MH. Phosphorus, Sulfur Silicon Relat. Elem. 2020; 195 (03) 181
• 27 Hardy FE, Speakman PR. H, Robson P. J. Chem. Soc. C 1969; 2334