Communication
ChemComm
(c) A. E. Wendlandt, A. M. Suess and S. S. Stahl, Angew. Chem., Int.
Ed., 2011, 50, 11062–11087.
5882–5890; (e) J. Xu, Y. Fu, D.-F. Luo, Y.-Y. Jiang, B. Xiao, Z.-J. Liu,
T.-J. Gong and L. Liu, J. Am. Chem. Soc., 2011, 133, 15300–15303.
3 X. Chen, X.-S. Hao, C. E. Goodhue and J.-Q. Yu, J. Am. Chem. Soc., 10 It is worth noting that the unactivated C(sp3)–H bonds can be
2006, 128, 6790–6791.
activated in some radical reactions. But high regioselectivity is
obtained only with limited simple alkanes. It is also crucial to use
excess alkyl substrates (even as solvent) to achieve synthetically
useful yields. For selected examples, see: (a) R. T. Gephart, D. L.
Huang, M. J. B. Aguila, G. Schmidt, A. Shahu and T. H. Warren,
Angew. Chem., Int. Ed., 2012, 51, 6488–6492; (b) B. L. Tran, B. Li,
M. Driess and J. F. Hartwig, J. Am. Chem. Soc., 2014, 136, 2555–2563;
(c) P. K. Chikkade, Y. Kuninobu and M. Kanai, Chem. Sci., 2015, 6,
3195–3200; (d) B. L. Tran, M. Driess and J. F. Hartwig, J. Am. Chem.
Soc., 2014, 136, 17292–17301.
4 Selected examples on copper-mediated C(sp2)–H activation/C–C
bond formation: (a) H.-Q. Do and O. Daugulis, J. Am. Chem. Soc.,
2008, 130, 1128–1129; (b) H.-Q. Do and O. Daugulis, J. Am. Chem.
Soc., 2011, 133, 13577–13586; (c) H.-Q. Do, R. M. K. Khan and
O. Daugulis, J. Am. Chem. Soc., 2008, 130, 15185–15192; (d) M. Kitahara,
N. Umeda, K. Hirano, T. Satoh and M. Miura, J. Am. Chem. Soc., 2011, 133,
2160–2162; (e) M. Nishino, K. Hirano, T. Satoh and M. Miura, Angew.
Chem., Int. Ed., 2012, 51, 6993–6997; ( f ) M. Nishino, K. Hirano, T. Satoh
and M. Miura, Angew. Chem., Int. Ed., 2013, 52, 4457–4461; (g) R. Odani,
K. Hirano, T. Satoh and M. Miura, Angew. Chem., Int. Ed., 2014, 53, 11 Previous reports on copper-mediated directed unactivated C(sp3)–H
10784–10788; (h) I. Popov, S. Lindeman and O. Daugulis, J. Am. Chem.
Soc., 2011, 133, 9286–9289; (i) M. Shang, S.-Z. Sun, H.-L. Wang,
B. N. Laforteza, H.-X. Dai and J.-Q. Yu, Angew. Chem., Int. Ed., 2014, 53,
10439–10442; ( j) M. Shang, H.-L. Wang, S.-Z. Sun, H.-X. Dai and J.-Q. Yu,
J. Am. Chem. Soc., 2014, 136, 11590–11593.
bond functionalization: (a) Z. Wang, J. Ni, Y. Kuninobu and
M. Kanai, Angew. Chem., Int. Ed., 2014, 53, 3496–3499; (b) X. Wu,
Y. Zhao, G. Zhang and H. Ge, Angew. Chem., Int. Ed., 2014, 53,
3706–3710; (c) X. Wu, Y. Zhao and H. Ge, Chem. Sci., 2015, 6,
5978–5983; (d) X. Wu, Y. Zhao and H. Ge, Chem. – Asian J., 2014,
9, 2736–2739; (e) Z. Wang, Y. Kuninobu and M. Kanai, Org. Lett.,
2014, 16, 4790–4793; ( f ) J. Zhang, H. Chen, B. Wang, Z. Liu and
Y. Zhang, Org. Lett., 2015, 17, 2768–2771.
5 Selected examples on copper-mediated C(sp2)–H activation/C–N
bond formation: (a) L. D. Tran, J. Roane and O. Daugulis, Angew.
Chem., Int. Ed., 2013, 52, 6043–6046; (b) T. Kawano, K. Hirano,
T. Satoh and M. Miura, J. Am. Chem. Soc., 2010, 132, 6900–6901; 12 (a) D. Shabashov and O. Daugulis, J. Am. Chem. Soc., 2010, 132,
(c) M. Shang, S.-Z. Sun, H.-X. Dai and J.-Q. Yu, J. Am. Chem. Soc.,
2014, 136, 3354–3357; (d) Q. Li, S.-Y. Zhang, G. He, Z. Ai, W. A. Nack
3965–3972; (b) V. G. Zaitsev, D. Shabashov and O. Daugulis, J. Am.
Chem. Soc., 2005, 127, 13154–13155.
and G. Chen, Org. Lett., 2014, 16, 1764–1767; (e) K. Takamatsu, 13 Recent reports on copper-mediated aerobic oxidation: (a) L. Zhang,
K. Hirano, T. Satoh and M. Miura, Org. Lett., 2014, 16, 2892–2895.
6 Selected examples on copper-mediated C(sp2)–H activation/C–O
bond formation: (a) S. Bhadra, W. I. Dzik and L. J. Gooßen, Angew.
Chem., Int. Ed., 2013, 52, 2959–2962; (b) S. Bhadra, C. Matheis,
D. Katayev and L. J. Gooßen, Angew. Chem., Int. Ed., 2013, 52,
9279–9283; (c) A. M. Suess, M. Z. Ertem, C. J. Cramer and S. S.
Stahl, J. Am. Chem. Soc., 2013, 135, 9797–9804; (d) J. Roane and
X. Bi, X. Guan, X. Li, Q. Liu, B.-D. Barry and P. Liao, Angew. Chem.,
Int. Ed., 2013, 52, 11303–11307; (b) J. E. Steves and S. S. Stahl, J. Am.
Chem. Soc., 2013, 135, 15742–15745; (c) S. D. McCann and S. S. Stahl,
Acc. Chem. Res., 2015, 48, 1756–1766; (d) C. Tang and N. Jiao, Angew.
Chem., Int. Ed., 2014, 53, 6528–6532; (e) X. Huang, X. Li, M. Zou,
S. Song, C. Tang, Y. Yuan and N. Jiao, J. Am. Chem. Soc., 2014, 136,
14858–14865.
O. Daugulis, Org. Lett., 2013, 15, 5842–5845; (e) N. Takemura, 14 (a) S. Schwarz, S. D. Lucas, S. Sommerwerk and R. Csuk, Bioorg. Med.
Y. Kuninobu and M. Kanai, Org. Lett., 2013, 15, 844–847.
Chem., 2014, 22, 3370–3378; (b) Z. Lin, Y. Guo, Y. Gao, S. Wang,
X. Wang, Z. Xie, H. Niu, W. Chang, L. Liu, H. Yuan and H. Lou,
J. Med. Chem., 2015, 58, 3944–3956; (c) C. Spencer and L. Barradell,
Drugs, 1996, 51, 982–1018.
7 Selected examples on copper-mediated C(sp2)–H activation/C–X
(X = halogen) bond formation: (a) A. M. Suess, M. Z. Ertem,
C. J. Cramer and S. S. Stahl, J. Am. Chem. Soc., 2013, 135,
9797–9804; (b) T. Truong, K. Klimovica and O. Daugulis, J. Am. 15 (a) S. Monge, V. Darcos and D. M. Haddleton, J. Polym. Sci., Part A:
Chem. Soc., 2013, 135, 9342–9345; (c) B. Urones, A. M. Martinez,
N. Rodriguez, R. G. Arrayas and J. C. Carretero, Chem. Commun.,
Polym. Chem., 2004, 42, 6299–6308; (b) S. S. Stahl, Science, 2005, 309,
1824–1826.
2013, 49, 11044–11046; (d) B. Li, B. Liu and B.-F. Shi, Chem. 16 (a) C.-J. Wallentin, J. D. Nguyen, P. Finkbeiner and C. R. J.
Commun., 2015, 51, 5093–5096.
Stephenson, J. Am. Chem. Soc., 2012, 134, 8875–8884; (b) D. M.
Smith, M. E. Pulling and J. R. Norton, J. Am. Chem. Soc., 2007, 129,
770–771; (c) D. Yang, S. Gu, Y.-L. Yan, N.-Y. Zhu and K.-K. Cheung,
J. Am. Chem. Soc., 2001, 123, 8612–8613.
8 Selected examples on copper-mediated C(sp2)–H activation/C–S
bond formation: (a) L. D. Tran, I. Popov and O. Daugulis, J. Am.
Chem. Soc., 2012, 134, 18237–18240; (b) F.-J. Chen, G. Liao, X. Li,
J. Wu and B.-F. Shi, Org. Lett., 2014, 16, 5644–5647; (c) W.-H. Rao and 17 R. Shang, L. Ilies, A. Matsumoto and E. Nakamura, J. Am. Chem. Soc.,
B.-F. Shi, Org. Lett., 2015, 17, 2784–2787. 2013, 135, 6030–6032.
9 Selected examples on copper-mediated activated C(sp3)–H function- 18 When substrate 8 was subjected to the standard reaction condi-
alization: (a) Z. Li and C.-J. Li, J. Am. Chem. Soc., 2006, 128, 56–57; tions, the demethylation product 7a was obtained in 45% yield.
(b) G. Zhang, Y. Zhao and H. Ge, Angew. Chem., Int. Ed., 2013, 52, 19 For early studies on directed aerobic oxidation with copper catalysts, see:
¨ ¨
(a) B. Schonecker, T. Zheldakova, Y. Liu, M. Kotteritzsch, W. Gu¨nther and
2559–2563; (c) X. Wang, Y. Ye, S. Zhang, J. Feng, Y. Xu, Y. Zhang and
J. Wang, J. Am. Chem. Soc., 2011, 133, 16410–16413; (d) X. Wu,
M. Wang, G. Zhang, Y. Zhao, J. Wang and H. Ge, Chem. Sci., 2015, 6,
¨
H. Gorls, Angew. Chem., Int. Ed., 2003, 42, 3240–3244; (b) Y. L. Tnay,
C. Chen, Y. Y. Chua, L. Zhang and S. Chiba, Org. Lett., 2012, 14, 3550–3553.
Chem. Commun.
This journal is ©The Royal Society of Chemistry 2015