Communication
Green Chemistry
Notes and references
1 (a) Y. Wang, Y. Li and X. Jiang, Chem. – Asian J., 2018, 13,
2208; (b) M. Feng, B. Tang, S. Liang and X. Jiang, Curr. Top.
Med. Chem., 2016, 16, 1200; (c) H. Liu and X. Jiang, Chem. –
Asian J., 2013, 8, 2546; (d) S. Mukherjee, H. Verma and
J. Chatterjee, Org. Lett., 2015, 17, 3150; (e) K. Fukumoto,
A. Sakai, K. Hayasaka and H. Nakazawa, Organometallics,
2013, 32, 2889; (f) J. Hwang, M. G. Choi, S. Eor and
S. Chang, Inorg. Chem., 2012, 51, 1634; (g) Z. Qiao and
X. Jiang, Org. Biomol. Chem., 2017, 15, 1942; (h) A. Okano,
R. C. James, J. G. Pierce, J. Xie and D. L. Boger, J. Am.
Chem. Soc., 2012, 134, 8790; (i) M. Wang and X. Jiang, Top.
Curr. Chem., 2018, 376, 14.
2 (a) N. Wang, J. Liu, C. Wang, L. Bai and X. Jiang, Org. Lett.,
2018, 20, 292; (b) N. Wang, S. Du, D. Li and X. Jiang, Org.
Lett., 2017, 19, 3167; (c) B. A. D. Neto, A. A. M. Lapis,
A. B. Bernd and D. Russowsky, Tetrahedron, 2009, 65, 2484;
(d) F. Hermant, E. Urbańska, S. S. de Mazancourt,
T. Maubert, E. Nicolas and Y. Six, Organometallics, 2014, 33,
5643; (e) E. Augustowska, A. Boiron, J. Deffit and Y. Six,
Chem. Commun., 2012, 48, 5031.
3 (a) A. H. Beesley, M. J. Firth, D. Anderson, A. L. Samuels,
J. Ford and U. R. Kees, Cancer Res., 2013, 73, 2749;
(b) X. Liu, R. C. Hatton, Y. Zhu, J. M. Hincapie-Castillo,
R. Bussing, M. Barnicoat and A. G. Winterstein, J. Am.
Pharm. Assoc., 2017, 57, 698; (c) P. Angehrn, E. Goetschi,
H. Gmuender, P. Hebeisen, M. Hennig, B. Kuhn,
T. Luebbers, P. Reindl, F. Ricklin and A. Schmitt-
Hoffmann, J. Med. Chem., 2011, 54, 2207.
4 (a) T. Lincke, S. Behnken, K. Ishida, M. Roth and C. Hertweck,
Angew. Chem., Int. Ed., 2010, 49, 2011; (b) A. Bach,
J. N. N. Eildal, N. Stuhr-Hansen, R. Deeskamp, M. Gottschalk,
S. W. Pedersen, A. S. Kristensen and K. Strømgaard, J. Med.
Chem., 2011, 54, 1333; (c) S. P. Ebert, B. Wetzel, R. L. Myette,
G. Conseil, S. P. C. Cole, G. A. Sawada, T. W. Loo, M. C. Bartlett,
D. M. Clarke and M. R. Detty, J. Med. Chem., 2012, 55, 4683;
(d) J. Li, X. Ren, G. Li, H. Liang, Y. Zhao, Z. Wang, H. Li and
B. Yuan, J. Sulfur Chem., 2020, 41, 229.
Fig. 4 Influence of the C state on our C(sp3)–H thiocarbonylation
(mechanistic studies 3).
the computational stable C state and some experimental by-
products.
Conclusions
In summary, based on the “solvent-specificity-based” design
strategy, we have developed a solvent-driven C(sp3)–H thiocar-
bonylation of benzylamine derivatives, which proceeded
efficiently for thioamide synthesis under catalyst-free, opera-
tionally simple and environmentally friendly conditions. A
wide variety of substituents on the benzylamine substrates
were tolerated by our thiocarbonylation with excellent yields.
Our methodology is worth noting in that it cleverly utilized the
specificities of solvent instead of the property of the previously
reported metal catalyst to drive the C(sp3)–H thiocarbonylation
and got a good result. Given this, further studies on the appli-
cation of solvent specificities are ongoing in our laboratories.
In addition, our thiocarbonylation may play a role in the site-
directed thiocarbonylation since it focuses on the benzylamine
substrate and is almost unaffected by the substituents on the
benzylamine substrate, such as achieving the site-directed
thiocarbonylation of some compounds containing multiple
thiocarbonylation sites.
5 (a) A. Manaka and M. Sato, Synth. Commun., 2005, 35, 761;
(b) A. K. Yadav, V. P. Srivastava and L. D. S. Yadav,
Tetrahedron Lett., 2012, 53, 7113.
6 (a) T. Jagodzinski, E. Jagodzinska and Z. Jabłonski,
Tetrahedron, 1986, 42, 3683; (b) T. Jagodzinski, Synthesis,
1988, 717; (c) B. V. Varun, A. Sood and K. R. Prabhu, RSC
Adv., 2014, 4, 60798.
Conflicts of interest
There are no conflicts to declare.
7 (a) O. I. Zbruyev, N. Stiasni and C. O. Kappe, J. Comb.
Chem., 2003, 5, 145; (b) L. D. Priebbenow and C. Bolm,
Chem. Soc. Rev., 2013, 42, 7870; (c) T. Guntreddi, R. Vanjari
and K. N. Singh, Org. Lett., 2014, 16, 3624; (d) Y. Qu, Z. Li,
H. Xiang and X. Zhou, Adv. Synth. Catal., 2013, 355, 3141;
(e) P. Zhang, W. Chen, M. Liu and H. Wu, J. Org. Chem.,
2018, 83, 14269; (f) L. Gan, Y. Gao, L. Wei and J.-P. Wan,
J. Org. Chem., 2019, 84, 1064.
Acknowledgements
This work was supported by the National Science Foundation
of China (81803436 and 21702236) And Guangzhou Science
Technology and Innovation Commission Technology Research
Projects
(201805010005).
We
thank
the
National
Supercomputing Center in Guangzhou for providing the com-
putational resources. We also thank Prof. Ruibo Wu at SYSU
for his help in mechanism analysis.
8 (a) H. Xu, H. Deng, Z. Li, H. Xiang and X. Zhou, Eur. J. Org.
Chem., 2013, 7054; (b) T. B. Nguyen, M. Q. Tran,
772 | Green Chem., 2021, 23, 767–773
This journal is © The Royal Society of Chemistry 2021