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Chemical Science
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Journal Name
ARTICLE
We have developed a novel, efficient and generally-applicable
approach for the chemo- and stereoselective alkylation of enamides
with NHP esters. A wide array of enamides and NHP esters bearing
various functional groups were viable to this protocol to afford
synthetically important and geometrically-defined enamides
bearing primary secondary or tertiary alkyl groups in moderate to
good yields and excellent stereoselectivities. A plethora of further
transformations were applied to showcase the synthetical value of
this transformation. A radical reaction pathway was proposed
through mechanistic investigation. The simple operation and the
easy availability of the starting materials also allowed this method
to pave a new route for the preparation of synthetically crucial
alkylated enamides.
China Chem., 2016, 59, 195.
6
G. Caillot, J. Dufour, M.-C. Belhomme, DTO. PI:o1i0s.s1o03n9,/LC.9GSCri0m30a7u0dK,
X. Pannecoucke and I. Gillaizeau, Chem. Commun., 2014, 50,
5887.
C. Feng, D. Feng and T.-P. Loh, Chem. Commun., 2014, 50,
9865.
(a) K. D. Hesp, R. G. Bergman and J. A. Ellman, J. Am. Chem.
Soc., 2011, 133, 11430; (b) H. Wang, L.-N. Guo and X.-H.
Duan, Org. Lett., 2012, 14, 4358; (c) R. Ding, Q.-C. Zhang, Y.-
H. Xu and T.-P. Loh, Chem. Commun., 2014, 50, 11661; (d) Z.
Xiong, D. Liang and S. Luo, Org. Chem. Front., 2017, 4, 1103.
(a) Y. Li, K. Cheng, X. Lu and J. Sun, Adv. Synth. Catal., 2010,
352, 1876; (b) D. Sun and R. Zhang, Org. Chem. Front., 2018,
5, 92; (c) T.-H. Zhu, X.-C. Zhang, K. Zhao, T.-P. Loh, Org. Chem.
Front., 2019, 6, 94. (d) T.-H. Zhu, X.-C. Zhang, X.-L. Cui, Z.-Y.
Zhang, H. Jiang, S.-S. Sun, L.-L. Zhao, K. Zhao, T.-P. Loh, Adv.
Synth. & Catal. 2019, DOI: 10.1002/adsc.201900257.
7
8
9
Conflicts of interest
10 W. Yu, J. Chen, K. Gao, Z. Liu, Y. Zhang, Org. Lett., 2014, 16,
4870.
The authors declare no competing financial interest.
11 (a) H. Jiang, C. Huang, J. Guo, C. Zeng, Y. Zhang and S. Yu,
Chem. Eur. J., 2012, 18, 15158; (b) R. Ding, Z.-D. Huang, Z.-L.
Liu, T.-X. Wang, Y.-H. Xu and T.-P. Loh, Chem. Commun.,
2016, 52, 5617; (c) D. Xing and G. Dong, J. Am. Chem. Soc.,
2017, 139, 13664; (d) C. Baudequin, A. Zamfir and S. B.
Tsogoeva, Chem. Commun., 2008, 0, 4637; (e) B. Maji, S.
Lakhdar and H. Mayr, Chem. Eur. J., 2012, 18, 5732; (f) M.-N.
Zhao, W. Du, Z.-H. Ren, Y.-Y. Wang and Z.-H. Guan, Eur. J.
Org. Chem., 2013, 7989; (g) P. Li, J. Zhao, C. Xia and F. Li, Org.
Lett., 2014, 16, 5992; (h) M. Giedyk, K. Goliszewska, K. ó.
Proinsias and D. Gryko, Chem. Commun., 2016, 52, 1389.
12 (a) K. Okada, K. Okamoto and M. Oda, J. Am. Chem. Soc.,
1988, 110, 8736; (b) K. Okada, K. Okamoto and M. Oda, J.
Chem. Soc. Chem. Commun., 1989, 1636; (c) K. Okada, K.
Okamoto, N. Morita, K. Okubo and M. Oda, J. Am. Chem. Soc.,
1991, 113, 9401; (d) K. Okada, K. Okubo, N. Morita and M.
Oda, Tetrahedron Lett., 1992, 33, 7377; (e) K. Okada, K.
Okubo, N. Morita and M. Oda, Chem. Lett., 1993, 22, 2021.
13 (a) C. R. Jamison and L. E. Overman, Acc. Chem. Res., 2016,
49, 1578; (b) D. J. Tao, Y. Slutskyy, M. Muuronen, A. Le, P.
Kohler and L. E. Overman, J. Am. Chem. Soc., 2018, 140, 3091;
(c) M. R. Garnsey, Y. Slutskyy, C. R. Jamison, P. Zhao, J. Lee, Y.
H. Rhee and L. E. Overman J. Org. Chem., 2018, 83, 6958.
14 For selected examples on transition metal-catalyzed C(sp3)-C
formation, see: (a) J. Cornella, J. T. Edwards, T. Qin, S.
Kawamura, J. Wang, C.-M. Pan, R. Gianatassio, M. Schmidt,
M. D. Eastgate and P. S. Baran, J. Am. Chem. Soc., 2016, 138,
2174; (b) T. Qin, J. Cornella, C. Li, L. R. Malins, J. T. Edwards,
S. Kawamura, B. D. Maxwell, M. D. Eastgate and P. S. Baran,
Science, 2016, 352, 801; (c) F. Toriyama, J. Cornella, L.
Wimmer, T.-G. Chen, D. D. Dixon, G. Creech and P. S. Baran,
J. Am. Chem. Soc., 2016, 138, 11132; (d) T. Qin, L. R. Malins,
J. T. Edwards, R. R. Merchant, A. J. E. Novak, J. Z. Zhong, R. B.
Mills, M. Yan, C. Yuan, M. D. Eastgate and P. S. Baran,
Angew. Chem., Int. Ed., 2017, 56, 260; (e) J. M. Smith, T. Qin,
R. R. Merchant, J. T. Edwards, L. R. Malins, Z. Liu, G. Che, Z.
Shen, S. A. Shaw, M. D. Eastgate and P. S. Baran, Angew.
Chem., Int. Ed., 2017, 56, 11906; (f) J. T. Edwards, R. R.
Merchant, K. S. McClymont, K. W. Knouse, T. Qin, L. R.
Malins, B. Vokits, S. A. Shaw, D.-H. Bao, F.-L. Wei, T. Zhou, M.
D. Eastgate and P. S. Baran, Nature, 2017, 545, 213; (g) S. Ni,
A. F. Garrido-Castro, R. R. Merchant, J. N. de Gruyter, D. C.
Schmitt, J. J. Mousseau, G. M. Gallego, S. Yang, M. R. Collins,
J. X. Qiao, K.-S. Yeung, D. R. Langley, M. A. Poss, P. M. Scola,
T. Qin and P. S. Baran, Angew. Chem., Int. Ed., 2018, 57,
14560; (h) K. M. M. Huihui, J. A. Caputo, Z. Melchor, A. M.
Olivares, A. M. Spiewak, K. A. Johnson, T. A. DiBenedetto, S.
Kim, L. K. G. Ackerman and D. J. Weix, J. Am. Chem. Soc.,
Acknowledgements
We gratefully acknowledge the financial support from Nanjing Tech
University (Start-up Grant No. 39837137, 39837101 and
3827401739), National Natural Science Foundation of China
(21372210, 21672198, 21801129), the State Key Program of
National Natural Science Foundation of China (21432009), and
Natural science research projects in Jiangsu higher education
institutions (18KJB150018) for financial support.
References
1
(a) R. Matsubara and S. Kobayashi, Acc. Chem. Res., 2008, 41,
292; (b) C. Curti, M. Laget, A. O. Carle, A. Gellis and P.
Vanelle, Eur. J. Med. Chem., 2007, 42, 880; (c) H. Yang, R. G.
Carter and L. N. Zakharov, J. Am. Chem. Soc., 2008, 130, 9238;
(d) J.-H. Xie, S.-F. Zhu and Q.-L. Zhou, Chem. Rev., 2011, 111,
1713; (e) K. Gopalaiah and H. B. Kagan, Chem. Rev., 2011,
111, 4599.
2
(a) S. Tong, D.-X. Wang, L. Zhao, J. Zhu and M.-X. Wang,
Angew. Chem., Int. Ed., 2012, 51, 4417; (b) M.-N. Zhao, Z.-H.
Ren, Y.-Y. Wang and Z.-H. Guan, Chem. Commun., 2012, 48,
8105; (c) G. Liu, X. Liu, Z. Cai, G. Jiao, G. Xu and W. Tang,
Angew. Chem., Int. Ed., 2013, 52, 4235; (d) C.-H. Lei, D.-X.
Wang, L. Zhao, J. Zhu and M.-X. Wang, J. Am. Chem. Soc.,
2013, 135, 4708; (e) M.-N. Zhao, Z.-H. Ren, Y.-Y. Wang and
Z.-H. Guan, Org. Lett., 2014, 16, 608; (f) C.-H. Lei, L. Zhao, D.-
X. Wang, J. Zhu and M.-X. Wang, Org. Chem. Front., 2014, 1,
909; (g) N. Hu, G. Zhao, Y. Zhang, X. Liu, G. Li and W. Tang, J.
Am. Chem. Soc., 2015, 137, 6746; (h) P. Song, P. Yu, J.-S. Lin,
Y. Li, N.-Y. Yang and X.-Y. Liu, Org. Lett. 2017, 19, 1330.
(a) S. Pankajakshan, Y.-H. Xu, J. K. Cheng, M. T. Low and T.-P.
Loh, Angew. Chem., Int. Ed., 2012, 51, 5701; (b) H.-L. Wang,
R.-B. Hu, H. Zhang, A.-X. Zhou and S.-D. Yang, Org. Lett.,
2013, 15, 5302; (c) F. Bartoccini, D. M. Cannas, F. Fini and G.
Piersanti, Org. Lett., 2016, 18, 2762; (d) N. Gigant, L.
Chausset-Boissarie, M. Belhomme, T. Poisson, X.
Pannecoucke, I. Gillaizeau, Org. Lett., 2013, 15, 278.
3
4
5
(a) T. Besset, N. Kuhl, F. W. Patureau and F. Glorius, Chem.
Eur. J., 2011, 17, 7167; (b) Y.-H. Xu, Y. K. Chok and T.-P. Loh,
Chem. Sci., 2011, 2, 1822; (c) N. Gigant and I. Gillaizeau, Org.
Lett., 2012, 14, 3304; (d) W. Zhu, L. Zhao and M.-X. Wang, J.
Org. Chem., 2015, 80, 12047.
(a) C. Feng and T.-P. Loh, Chem. Sci., 2012, 3, 3458; (b) R.
Rey-Rodriguez, P. Retailleau, P. Bonnet, I. Gillaizeau, Chem.
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