Angewandte Chemie International Edition
10.1002/anie.201706804
COMMUNICATION
Overall, these results are in support of the reaction sequence
postulated in Figure 1c, whereby the C–H cleavage would be
reversible and the protodemetalation turnover-limiting.
Satoh, M. Miura, Angew. Chem. Int. Ed. 2012, 51, 775; Angew. Chem.
2012, 124, 799; d) F. Ye, X. Ma, Q. Xiao, H. Li, Y. Zhang, J. Wang, J.
Am. Chem. Soc. 2012, 134, 5742.
[
7]
a) T. K. Hyster, T. Rovis, Synlett 2013, 1842; b) H. Zhang, K. Wang, B.
Wang, H. Fi, F. Hu, C. Li, Y. Zhang, J. Wang, Angew. Chem. Int. Ed.
2014, 53, 13234; Angew. Chem. 2014, 126, 13450.
In conclusion, the cross-coupling described herein expands
the traditional chemistry of sulfoxonium ylides[20] and brings these
reagents into the realm of metal-catalyzed C–H activation.[21,22]
[8]
9]
S. Y. Hong, J. Jeong, S. Chang, Angew. Chem. Int. Ed. 2017, 56, 2408;
Angew. Chem. 2017, 129, 2448.
[
a) H. M. L. Davies, J. R. Manning, Nature 2008, 451, 417; b) M. P. Doyle,
R. Duffy, M. Ratnikov, L. Zhou, L. Chem. Rev. 2010, 110, 704.
Acknowledgements
[10] L. L. William, W. W. Brennessel, W. D. Jones, J. Am. Chem. Soc. 2008,
30, 12414.
1
[
11] CCDC 1557332 (3) and CCDC 1557333 (4) contains the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
We are grateful to the University of Liverpool (studentships to M.
B. and C. J.) and AstraZeneca (CASE award to C. J.) for financial
support. We thank Umicore for the generous gift of rhodium salts.
[
12] 7: 2-(3-methoxyphenyl)pyridine; 8: ethyl 3-(pyridin-2-yl)benzoate; 9: 1-
(pyridin-2-yl)-1H-indole; 10: 2-(1H-pyrrol-1-yl)pyridine; 11: 2-(furan-3-
yl)pyridine; 12: 2H-[1,2'-bipyridin]-2-one; 13: 1-phenyl-1H-pyrazole; 14:
Keywords: Sulfoxonium • Ylide • C–H activation • rhodium •
homogeneous catalysis
1-(pyrimidin-2-yl)-1H-indole; 15: 2-(furan-3-yl)pyrimidine; 16: (E)-1-
phenylethan-1-one O-methyl oxime.
[
[
1]
2]
a) J. E. Baldwin, R. M. Adlington, C. R. A. Godfrey, D. W. Gollins, J. G.
Vaughan, J. Chem. Soc., Chem. Commun. 1993, 1434; b) A. I. O. Suarez,
M. P. del Rio, K. Remerie, J. N. H. Reek, B. de Bruin, ACS Catal. 2012,
[
13] a) J, Shi, Y. Yan, Q. Li, H. E. Xu, W. Yi, Chem. Commun. 2014, 50, 6483;
b) W. Ai, X. Yang, Y. Wu, X. Wang, Y. Li, Y, Yang, B. Zhou, Chem. Eur.
J. 2014, 20, 17653. For alternative reagents, see: c) X. Zhang, Z. Qi, X.
Li, Angew. Chem. Int. Ed. 2014, 53, 10794; Angew. Chem. 2014, 126,
2, 2046.
a) I. K. Mangion, I. K. Nwamba, M. Shevlin, M. A. Huffman, Org. Lett.
1
0970; d) Y Hara, S. Onodera, T. Kochi, F. Kakiuchi, Org. Lett. 2015, 17,
850. With [{Cp*IrCl ] catalyst, see: e) Y. Xia, Z. Liu, S. Feng, Y. Zhang,
2009, 11, 3566; b) I. K. Mangion, M. Weisel Tetrahedron Lett. 2010, 51,
4
2 2
}
5490; c) I. K. Mangion, R. T. Ruck, N. Nivera, M. A. Huffmanm, M.
J. Wang, J. Org. Chem. 2015, 80, 223.
Shevlin, Org. Lett. 2011, 13, 5480; d) C. Molinaro, P. G. Bulger, E. E.
Lee, B. Kosjek, S. Lau, D. Gauvreau, M. E. Howard, D. J. Wallace, P. D.
O’Shea, J. Org. Chem. 2012, 77, 2299; e) N. Wishart, D. F. Bonafoux, K.
E. Frank, A. D. Hobson, D. B. Konopacki, G. Y. Martinez, L. Wang, US
[
14] For a similar approach with α-(pseudo)halo ketones, see D.-G. Yu, F de
Azambuja, F. Glorius, Angew. Chem. Int. Ed. 2014, 53, 2754; Angew.
Chem. 2014, 126, 2792.
[
[
15] K.-i. Fujita, C. Kitatsuji, S. Kurukawa, R. Yamaguchi, Tetrahedron Lett.
21030072470 A1; f) R. D. Tung, A. J. Morgan, WO 2104022390 A1; g)
2004, 45, 3215.
A. M. Phelps, V. S. Chan, J. G. Napolitano, S. W. Krabbe, J. M.
Schomaker, S. Shekhar, J. Org. Chem. 2016, 81, 4158.
16] a) D. Makhey, C. Yu, A. Liu, L. F. Liu, E. J. LaVoie, Bioorg. Med. Chem.
2000, 8, 1171; b) J. Piechowska, D. T. Gryko, J. Org. Chem. 2011, 76,
10220; c) X. Pang, Z. Lou, M. Li, L. Wen, C. Chen, Eur. J. Org. Chem.
2015, 3361; d) G. C. Senadi, G. K. Dhandabai, W.-P. Hu, J.-J. Wang,
[
[
3]
4]
J. Vaitla, A. Bayer, K. H. Hopmann, Angew. Chem. Int. Ed. 2017, 56,
4277; Angew. Chem. 2017, 129, 4341.
Selected examples: a) W.-W. Chan, S.-F. Lo, Z. Zhou, W.-Y. Yu, J. Am.
Chem. Soc. 2012, 134, 13565; b) T. K. Hyster, K. E. Ruhl, T. Rovis, J.
Am. Chem. Soc. 2013, 135, 5364; c) X. Yu, S. Yu, B. Wan, X. Li, J. Org.
Chem. 2013, 78, 5444; d) Z. Shi, D. C. Koester, M. Boultadakis-Arapinis,
F. Glorius, J. Am. Chem. Soc. 2013, 135, 12204; e) S. Cui, Y. Zhang, D.
Wang, Q. Wu, Chem. Sci. 2013, 4, 3912; f) F. Hu, Y. Xia, F. Ye, Z. Liu,
C. Ma, Y. Zhang, J. Wang, Angew. Chem. Int. Ed. 2014, 53, 1364; Angew.
Chem. 2014, 126, 1388; g) B. Ye, N. Cramer, Angew. Chem. Int. Ed.
Green Chem. 2016, 18, 6241.
[
[
[
17] B. Zhang, X. Li, B. Li, C. Gao, Y. Jiang, Expert Opin. Ther. Patents 2014,
2
4, 647.
18] See supporting information for the location and amount of deuterium
transfer in 6a-D and 6b-D in these experiments.
n
n
19] a) M. E. Tauchert, C. D. Incarvito, A. L. Rheingold, R. G. Bergman, J. A.
Ellman, J. Am. Chem. Soc. 2012, 134, 1482; b) A. P. Walsh, W. D. Jones,
Organometallics 2015, 34, 3400; c) S. Qu, C. J. Cramer, J. Org. Chem.
2014, 53, 7896; Angew. Chem. 2014, 126, 8030; h) S. Yu, S. Liu, Y. Lan,
2017, 82, 1195.
B. Wan, X. Li, J. Am. Chem. Soc. 2015, 137, 1623; i) D. Zhao, J. H. Kim,
L. Stegemann, C. A. Strassert, F. Glorius, Angew. Chem. Int. Ed. 2015,
[
20] a) J.-F. Brière, P. Metzner in Organosulfur Chemistry in Asymmetric
Synthesis (Eds.: T. Toru, C. Bolm), Wiley-VCH, Weinheim, 2008, 179; b)
A. C. B. Burtoloso, R. M. P. Dias, I. A. Leonarczyk, Eur. J. Org. Chem.
5
4, 4508; Angew. Chem. 2015, 127, 4591; j) B. Zhou, Z. Chen, Y. Yang,
W. Ai, H. Tang, Y. Wu, W. Zhu, Y. Li, Angew. Chem. Int. Ed. 2015, 54,
2121; Angew. Chem. 2015, 127, 12289; k) J. Li, M. Tang, L. Zang, X.
2013, 5005.
1
[
21] Selected reviews: a) T. Satoh, M. Miura, Chem. Eur. J. 2010, 16, 11212;
b) J. Wencel-Delord, T. Dröge, F. Liu, F. Glorius, Chem. Soc. Rev. 2011,
Zhang, L. Ackermann, Org. Lett. 2016, 18, 2742; l) J. H. Kim, S. Greßies,
F. Glorius, Angew. Chem. Int. Ed. 2016, 55, 5577; Angew. Chem. 2016,
40, 4740; c) L. Ackermann, Chem. Rev. 2011, 111, 1315; d) K. M. Engle,
128, 5667; m) R. S. Phatake, P. Patel, C. V. Ramana, Org. Lett. 2016,
18, 292; n) Y. Li, Z. Qi, H. Wang, X. Yang, X. Li, Angew. Chem. Int. Ed.
2016, 55, 11877; Angew. Chem. 2016, 128, 12056; o) Z.-J. Jia, C.
T.-S. Mei, M. Wasa, J.-Q. Yu, Acc. Chem. Res. 2012, 45, 788; e) P. B.
Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev. 2012, 112, 5879; f) J.
Yamaguchi, A. D. Yamaguchi, K. Itami, Angew. Chem. Int. Ed. 2012, 51,
Merten, R. Gontla, C. G. Daniliuc, A. P. Antonchick, H. Waldmann,
Angew. Chem. Int. Ed. 2017, 56, 2429; Angew. Chem. 2017, 129, 2469.
J. H. Kim, T. Gensch, D. Zhao, L Stegemann, C. A. Strassert, F. Glorius,
F. Angew. Chem. Int. Ed. 2015, 54, 10975; Angew. Chem. 2015, 127,
8960; Angew. Chem. 2012, 124, 9092; g) G. Song, F. Wang, X. Li, Chem.
Soc. Rev. 2012, 41, 3651; h) N. Kuhl, N. Schröder, F. Glorius, Adv. Synth.
Catal. 2014, 356, 1443.
[
[
5]
6]
[
22] A report on the C–H activation of sulfoxonium ylides appeared during the
revision of this manuscript, see Y. Xu, X. Yang, X. Zhou, L. Kong, X. Li,
DOI: 10.1021/acs.orglett.7b01974.
1
1126.
a) Q. Xiao, Y. Xia, H. Li, Y. Zhang, J. Wang, Angew. Chem. Int. Ed. 2011,
0, 1114; Angew. Chem. 2011, 123, 1146; b) X. Zhao, G. Wu, Y. Zhang,
J. Wang, J. Am. Chem. Soc. 2011, 133, 3296; c) T. Yao, K. Hirano, T.
5
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