4
Commun. 2015, 51, 9969−9971. (h) Zhou, D.; Li, Z.-H.; Li, J.; Li,
decomposition of DTBP affords the initial tert-butoxyl radical
(tBuO), which then abstracts a hydrogen atom from acetonitrile
to produce cyanomethyl radical A.22 Esterification then proceeds
as follows: (a) A might react with [HSItBu][FeBr4] to generate
BrCH2CN and the initial Fe(II) species; (b) BrCH2CN could be
well-suited to react with 1a to afford desired product 3a (path a);
(c) the premier Fe(II) species is oxidized by DTBP to afford
active Fe(III) species B and tBuO; (d) through a metathesis
reaction between B and 1a, intermediate C can transform into
radical adduct D;23 (e) reductive elimination of D releases desired
product 3a and reforms the Fe(II) species, which can be oxidized
by DTBP for the next catalytic cycle (path b). The presence of an
imidazolinium cation with an electron-donating substituent on
the nitrogen atom might benefit the valence variation of iron.19a
S.-H.; Wang, M.-W.; Luo, X.-L.; Ding, G.-L.; Sheng, R.-L.; Fu,
M.-J.; Tang, S. Eur. J. Org. Chem. 2015, 1606−1612. (i) Tang, S.;
Zhou, D.; Li, Z.-H.; Fu, M.-J.; Li, J.; Sheng, R.-L.; Li, S.-H.
Synthesis 2015, 47, 1567−1580. (j) Tang, S.; Li, S.-H.; Li, Z.-H.;
Zhou, D.; Sheng, R.-L. Tetrahedron Lett. 2015, 56, 1423−1426. (k)
Chu, X.-Q.; Xu, X.-P.; Meng, H.; Ji, S.-J. RSC Adv. 2015, 5,
67829−67832. (l) Chu, X.-Q.; Xing, Z.-H.; Meng, H.; Xu, X.-P.; Ji,
S.-J. Org. Chem. Front. 2016, 3, 165−169. (m) Liu, Z.-Q.; Li, Z.
Chem. Commun. 2016, 52, 14278−14281. (n) Hu, M.; Zuo, H.-X.;
Song, R.-J.; Xiang, J.-N.; Li, J.-H. Org. Lett. 2016, 18, 6460−6463.
(o) Zhang, W.; Yang, S.; Shen, Z. Adv. Synth. Catal. 2016, 358,
2392−2397. (p) Ha, T. M.; Chatalova-Sazepin, C.; Wang, Q.; Zhu,
J. Angew. Chem., Int. Ed. 2016, 55, 9249−9252. (q) Ha, T. M.;
Wang, Q.; Zhu, J. Chem. Commun. 2016, 52, 11100−11103. (r)
Bunescu, A.; Ha, T. M.; Wang, Q.; Zhu, J. Angew. Chem., Int. Ed.
2017, 56, 10555−10558. (s) Wu, X.; Riedel, J.; Dong, V. M.
Angew. Chem., Int. Ed. 2017, 56, 11589−11593. (t) Zhu, N.; Wang,
T.; Ge, L.; Li, Y.; Zhang, X.; Bao, H. Org. Lett. 2017, 19,
4718−4721. (u) Li, Y.; Zhu, F.; Wang, Z.; Wu, X.-F. Chem.
Commun. 2018, 54, 1984−1987. (v) Shang, J.-Q.; Wang, S.-S.; Fu,
H.; Li, Y.; Yang, T.; Li, Y.-M. Org. Chem. Front. 2018, 5,
1945−1949.
Conclusions
In summary, we have developed a Fe(III)-catalyzed oxidative
coupling of alkylnitriles with aromatic carboxylic acids for the
preparation of cyanomethyl esters. This transformation is
outstanding for its inherent advantages, including nontoxic iron
catalysis, direct -C(sp3)–H bond oxidative esterification of
alkylnitriles, cheap and readily available substrates without
preestablished functional groups, and a wide substrate scope with
excellent steric hindrance tolerance. Further investigations into
the detailed reaction mechanism and other direct oxidative
functionalizations of -C(sp3)–H bonds in alkylnitriles are
currently underway in our laboratory.
6.
(a) Li, X.; Xu, J.; Gao, Y.; Fang, H.; Tang, G.; Zhao, Y. J. Org.
Chem. 2015, 80, 2621−2626. (b) Wu, H.; Yang, P.; Du, Z.; Fu, Y.
ChemistrySelect 2017, 2, 2183−2186.
Hu, M.; Li, M.; Tan, F.-L.; Song, R.-J.; Xie, Y.-X.; Li, J.-H. Adv.
Synth. Catal. 2017, 359, 120−129.
7.
8.
9.
Wang, K.; Chen, X.; Yuan, M.; Yao, M.; Zhu, H.; Xue, Y.; Luo, Z.;
Zhang, Y. J. Org. Chem. 2018, 83, 1525−1532.
(a) Pan, C.; Zhang, H.; Zhu, C. Org. Biomol. Chem. 2015, 13,
361−364. (b) Wang, C.; Li, Y.; Gong, M.; Wu, Q.; Zhang, J.; Kim,
J. K.; Huang, M.; Wu, Y. Org. Lett. 2016, 18, 4151−4153. (c)
Zhang, H.; Zhu, C. Org. Chem. Front. 2017, 4, 1272−1275. (d) Liu,
Y.-Y.; Yang, X.-H.; Song, R.-J.; Luo, S.; Li, J.-H. Nat. Commun.
2017, 8, 14720. (e) Su, H.; Wang, L.; Rao, H.; Xu, H. Org. Lett.
2017, 19, 2226−2229. (f) Qiao, K.; Zhang, D.; Zhang, K.; Yuan,
X.; Zheng, M.-W.; Guo, T.-F.; Fang, Z.; Wan, L.; Guo, K. Org.
Chem. Front. 2018, 5, 1129−1134.
Acknowledgements
This project was supported by the National Natural Science
Foundation of China (Grant No. 21472134), the Key Laboratory
of Organic Chemistry of Jiangsu Province, and the Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD).
10. Boukattaya, F.; Stanovych, A.; Setzer, P.; Abid, S.; Ammar, H.;
Pearson-Long, M. S. M.; Bertus, P. Chem. Commun. 2012, 48,
8655−8657.
11. (a) Setzer, P.; Beauseigneur, A.; Pearson-Long, M. S. M.; Bertus,
P. Angew. Chem., Int. Ed. 2010, 49, 8691−8694. (b) Setzer, P.;
Forcher, G.; Boeda, F.; Pearson-Long, M. S. M.; Bertus, P. Eur. J.
Org. Chem. 2014, 171−180.
References and Notes
12. Boukattaya, F.; Caillé, J.; Ammar, H.; Rouzier, F.; Boeda, F.;
Pearson-Long, M. S. M.; Bertus, P. Synthesis 2016, 48, 906−916.
13. Shen, R.; Lin, C. T.; Bowman, E. J.; Bowman, B. J.; Porco, J. A.;
Jr. J. Am. Chem. Soc. 2003, 125, 7889−7901.
14. Kim, S.; Kim, Y.; Kong, Y.; Kim, H.; Kang, J. Bioorg. Med. Chem.
Lett. 2009, 19, 508−512.
15. (a) Dreyer, D. L.; Tabata, S.; Horowitz, R. M. Tetrahedron 1964,
20, 2977−2983. (b) Nakamura, K.; Takenaka, K. Tetrahedron:
Asymmetry 2002, 13, 415−422. (c) Leroy, E.; Bensel, N.; Reymond,
J.-L. Adv. Synth. Catal. 2003, 345, 859−865.
16. For selected examples, see: (a) Ramaiah, M. J. Org. Chem. 1985,
50, 4991−4993. (b) Byers, J. H.; Baran, R. C.; Craig, M. E.;
Jackman, J. T. Org. Prep. Proced. Int. 1991, 23, 373−397. (c)
Hugela, H. M. Bhaskar, K. V. Longmore, R. W. Synth. Commun.
1992, 22, 693-697. (d) Wiklund, P.; Bergman, J. Tetrahedron Lett.
2004, 45, 969−972. (e) Bagal, S. K.; de Greef, M.; Zard, S. Z. Org.
Lett. 2006, 8, 147−150. (f) Gonçalves, M. S. T.; Oliveira-Campos,
A. M. F.; Rodrigues, L. M.; Proença, M. F. R. P. Synth. Commun.
2012, 42, 1695−1703. (g) Caillé, J.; Pantin, M.; Boeda, F.; Pearson-
Long, M. S. M.; Bertus, P. Synthesis 2019, 51, 1329−1341.
17. For selected examples, see: (a) Freskos, J. N.; Morrow, G. W.;
Swenton, J. S. J. Org. Chem. 1985, 50, 805−810. (b) Snider, B. B.;
Gao, X. J. Org. Chem. 2005, 70, 6863−6869. (c) Katritzky, A. R.;
Abdel-Fattah, A. A. A.; Idzik, K. R.; El-Gendy, B. E.-D. M.;
Soloducho, J. Tetrahedron 2007, 63, 6477−6484. (d) Nicolaou, K.
C.; Lu, M.; Chen, P.; Shah, A. A. Angew. Chem., Int. Ed. 2015, 54,
12687−12691. (e) Sk, M. R.; Chakraborty, S.; Mal, D. Synth.
Commun. 2018, 48, 309−317.
1. For selected examples, see: (a) Giri, R.; Shi, B.-F.; Engle, K. M.;
Maugel, N.; Yu, J.-Q. Chem. Soc. Rev. 2009, 38, 3242−3272. (b)
Baudoin, O. Chem. Soc. Rev. 2011, 40, 4902−4911. (c) Yeung, C.
S.; Dong, V. M. Chem. Rev. 2011, 111, 1215−1292. (d) Liu, C.;
Liu, D.; Lei, A. Acc. Chem. Res. 2014, 47, 3459−3470. (e) Liu, C.;
Yuan, J.; Gao, M.; Tang, S.; Li, W.; Shi, R.; Lei, A. Chem. Rev.
2015, 115, 12138−12204. (f) Crabtree, R. H.; Lei, A. Chem. Rev.
2017, 117, 8481−8482.
2.
For selected examples, see: (a) Mąkosza, M. Chem. Soc. Rev. 2010,
39, 2855−2868. (b) Velcicky, J.; Soicke, A.; Steiner, R.; Schmalz,
H.-G. J. Am. Chem. Soc. 2011, 133, 6948−6951. (c) Jinzaki, T.;
Arakawa, M.; Kinoshita, H.; Ichikawa, J.; Miura, K. Org. Lett.
2013, 15, 3750−3753. (d) Yi, H.; Zhang, X.; Qin, C.; Liao, Z.; Liu,
J.; Lei, A. Adv. Synth. Catal. 2014, 356, 2873−2877.
3.
For selected examples, see: (a) Fleming, F. F.; Yao, L.; Ravikumar,
P. C.; Funk, L.; Shook, B. C. J. Med. Chem. 2010, 53, 7902−7917.
(b) Trieselmann, T.; Wagner, H.; Fuchs, K.; Hamprecht, D.; Berta,
D.; Cremonesi, P.; Streicher, R.; Luippold, G.; Volz, A.; Markert,
M.; Nar, H. J. Med. Chem. 2014, 57, 8766−8776. (c) Ishikura, M.;
Abe, T.; Choshi, T.; Hibino, S. Nat. Prod. Rep. 2015, 32,
1389−1471.
4.
5.
(a) Wu, T.; Mu, X.; Liu, G. Angew. Chem., Int. Ed. 2011, 50,
12578−12581. (b) Deng, Z.; Peng, X.; Huang, P.; Jiang, L.; Ye, D.;
Liu, L. Org. Biomol. Chem. 2017, 15, 442−448.
(a) Shen, J.; Yang, D.; Liu, Y.; Qin, S.; Zhang, J.; Sun, J.; Liu, C.;
Liu, C.; Zhao, X.; Chu, C.; Liu, R. Org. Lett. 2014, 16, 350−353.
(b) Li, J.; Wang, Z.; Wu, N.; Gao, G.; You, J. Chem. Commun.
2014, 50, 15049−15051. (c) Bunescu, A.; Wang, Q.; Zhu, J. Chem.
- Eur. J. 2014, 20, 14633−14636. (d) Bunescu, A.; Wang, Q.; Zhu,
J. Angew. Chem., Int. Ed. 2015, 54, 3132−3135. (e) Bunescu, A.;
Wang, Q.; Zhu, J. Org. Lett. 2015, 17, 1890−1893. (f) Chatalova-
Sazepin, C.; Wang, Q.; Sammis, G. M.; Zhu, J. Angew. Chem., Int.
Ed. 2015, 54, 5443−5446. (g) Li, Z.; Xiao, Y.; Liu, Z.-Q. Chem.
18. Wang, H.; Shao, Y.; Zhao, H.; Wang, H.; Cheng, J.; Wan, X.
Chem. - Eur. J. 2015, 21, 18333−18337.
19. (a) Gao, H.-H.; Yan, C.-H.; Tao, X.-P.; Xia, Y.; Sun, H.-M.; Shen,
Q.; Zhang, Y. Organometallics 2010, 29, 4189−4192. (b) Li, Z.;
Liu, L.; Sun, H.-M.; Shen, Q.; Zhang, Y. Dalton Trans. 2016, 45,