Synlett, Table of Contents CC BY 4.0 · Synlett 2025; 36(07): 849-852DOI: 10.1055/a-2415-3708 letter Ruthenium(II)-Catalyzed C–H Allylation of N,N-Dialkylthiobenzamides with Allyl Methyl Carbonate by Sulfur Coordination Runbao Wang , Kun Jin , Rong Zhang , Yaming Li , Chunying Duan , Liang Zhao ∗ Recommend Article Abstract All articles of this category Abstract This report describes a Ru(II)-catalyzed C–H allylation of N,N-dialkylthiobenzamides with allyl methyl carbonate. The reaction is carried out using [RuCl2(p-cymene)]2 in the presence of Cu(OAc)2 and Ag2O. This method represents the first example of a Ru-catalyzed C–H allylation directed by a sulfur-containing group. As a further advantage, the method is performed in sustainable and ecofriendly MeCN as the solvent. Key words Key wordsC–H bond activation - directing group - ruthenium catalysis - allylation - thiobenzamides Full Text References References and Notes 1a Lakshman MK, Deb AC, Chamala RR, Pradhan P, Pratap R. Angew. Chem. Int. Ed. 2011; 50: 11400 1b Li Z.-K, Jia X.-S, Yin L. Synthesis 2018; 50: 4165 1c Rossi R, Lessi M, Manzini C, Bellina F. Adv. Synth. Catal. 2015; 357: 3777 2a Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068 2b Wencel-Delord J, Dröge T, Liu F, Glorius F. Chem. Soc. Rev. 2011; 40: 4740 2c Sambiagio C, Schönbauer D, Blieck R, Dao-Huy T, Pototschnig G, Schaaf P, Wiesinger T, Zia MF, Wencel-Delord J, Besset T, Maes BU. W, Schnürch M. Chem. Soc. Rev. 2018; 47: 6603 2d Sedelmeier G, Sedelmeier J. Chimia 2017; 71: 730 3a Wang P.-S, Gong L.-Z. Acc. Chem. Res. 2020; 53: 2841 3b Nobile E, Castanheiro T, Besset T. Angew. Chem. Int. Ed. 2021; 60: 12170 3c Tsuji J. Pure Appl. Chem. 1999; 71: 1539 3d Han JF, Guo P, Zhang X.-G, Liao J.-B, Ye K.-Y. Org. Biomol. Chem. 2020; 18: 7740 4a Chen Z, Wang B, Zhang J, Yu W, Liu Z, Zhang Y. Org. Chem. Front. 2015; 2: 1107 4b Zhu R.-Y, Farmer ME, Chen Y.-Q, Yu J.-Q. Angew. Chem. Int. Ed. 2016; 55: 10578 5a Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788 5b Park H, Li Y, Yu J.-Q. Angew. Chem. Int. Ed. 2019; 58: 11424 5c He J, Wasa M, Chan KS. L, Shao O, Yu J.-Q. Chem. Rev. 2017; 117: 8754 5d Zhang X.-G, Dai H.-X, Wasa M, Yu J.-Q. J. Am. Chem. Soc. 2012; 134: 11948 5e Li X, Zhang F, Wu D, Liu Y, Xu G, Peng Y, Liu Z, Huang Y. Tetrahedron 2018; 74: 7364 6a Li H.-L, Kanai M, Kuninobu Y. Org. Lett. 2017; 19: 5944 6b Rej S, Ano Y, Chatani N. Chem. Rev. 2020; 120: 1788 7 Kausar A, Zulfiqar S, Sarwar MI. Polym. Rev. 2014; 54: 185 8a Ilardi EA, Vitaku E, Njardarson JT. J. Med. Chem. 2014; 57: 2832 8b Beno BR, Yeung KS, Bartberger MD, Pennington LD, Meanwell NA. J. Med. Chem. 2015; 58: 4383 8c Liao Y, Wang M, Jiang X. Curr. Opin. Chem. Biol. 2023; 75: 102336 9a Saito M, Murakami S, Nanjo T, Kobayashi Y, Takemoto Y. J. Am. Chem. Soc. 2020; 142: 8130 9b Verma H, Khatri B, Chakraborti S, Chatterjee J. Chem. Sci. 2018; 9: 2443 9c Newberry RW, VanVeller B, Guzei IA, Raines RT. J. Am. Chem. Soc. 2013; 135: 7843 9d Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879 10 Park J, Mishra NK, Sharma S, Han S, Shin Y, Jeong T, Oh JS, Kwak JH, Jung YH, Kim IS. J. Org. Chem. 2015; 80: 1818 11 Yu D.-G, Gensch T, de Azambuja F, Vásquez-Céspedes S, Glorius F. J. Am. Chem. Soc. 2014; 136: 17722 12 Kim M, Sharma S, Mishra NK, Han S, Park J, Kim M, Shin Y, Kwak JH, Han SH, Kim IS. Chem. Commun. 2014; 50: 11303 13 Dutta S, Bhattacharya T, Werz DB, Maiti D. Chem 2021; 7: 555 14a Duan Y.-T, Wang Z.-X. J. Org. Chem. 2023; 88: 16076 14b Binnani C, Arora S, Priya B, Gupta P, Singh SK. Chem-Asian J. 2023; 18: 11 14c Zhang Y.-B, Li B.-S, Xu G.-J, Sun W, Sun M. Org. Lett. 2023; 25: 3922 14d Mondal S, Bera R, Chowdhury D, Dana S, Baidya M. Org. Lett. 2023; 25: 70 15 Allylation of N,N-Dialkylthiobenzamides; General Procedure A pressure tube was charged with [RuCl2(p-cymene)]2 (10 mol%), Cu(OAc)2 (2.0 equiv), Ag2O (0.5 equiv), K2CO3 (2.0 equiv), the appropriate N,N-dialkylthiobenzamide 1 (0.20 mmol, 1.0 equiv), and allyl methyl carbonate (2; 2.0 equiv). MeCN (1.5 mL) was then added with vigorous stirring at r.t. The tube was placed in an oil bath, and the mixture was stirred for the appropriate time at 100 °C. The mixture was then diluted with EtOAc (20 mL), filtered, and concentrated. The crude product was purified by column chromatography [silica gel, hexanes–EtOAc (10:1)]. 1-[(2-Allylphenyl)carbonothioyl]pyrrolidine (3a) Yellow oil; yield: 77%. 1H NMR (500 MHz, CDCl3): δ = 7.23 (d, J = 11.4 Hz, 3 H), 7.09 (d, J = 7.1 Hz, 1 H), 5.92 (ddd, J = 24.1, 9.0, 7.0 Hz, 1 H), 5.07 (dd, J = 24.7, 13.5 Hz, 2 H), 4.03 (dt, J = 13.8, 6.8 Hz, 1 H), 3.91 (dt, J = 14.2, 7.3 Hz, 1 H), 3.51 (dd, J = 15.2, 8.1 Hz, 1 H), 3.38 (dd, J = 15.2, 5.4 Hz, 1 H), 3.34–3.24 (m, 1 H), 3.26–3.11 (m, 1 H), 2.10–2.01 (m, 2 H), 1.93 (dp, J = 19.8, 6.5 Hz, 2 H). 13C NMR (126 MHz, CDCl3): δ = 196.58, 136.53, 133.84, 129.96, 128.81, 126.65, 124.86, 116.19, 53.03, 52.41, 37.18, 26.19, 24.60. HRMS (ESI): m/z [M + H]+ calcd for C14H18NS: 232.35; found: 232.19. Supplementary Material Supplementary Material Supporting Information
