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ChemComm
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arenes. We are very optimistic that with the ongoing progress
in dehydrogenative CHꢀcoupling and CHꢀactivation our two
step method using the reductive desulfurization of thiophenes
6
Alternative C(sp3)ꢀC(sp2)ꢀcouplings to introduce unfunctionalized
alkyl chains have been reported before. With alkyl halogenides: (a) L.
D. Tran and O. Dagulis, Org. Lett., 2010, 12, 4277. (b) L.
Ackermann, B. Punji and W. Song, Adv. Synth. Catal., 2011, 353,
3325. (c) L. Ackermann, Chem. Commun., 2010, 46, 4866. With
Grignard reagents: (d) P.ꢀY. Xin, H.ꢀY. Niu, G.ꢀR. Qu, R.ꢀF. Ding
and H.ꢀM. Guo, Chem. Commun., 2012, 48, 6717. With styrenes: (e)
W.ꢀC. Shih, W.ꢀC. Chen, Y.ꢀC. Lai, M.ꢀS. Yu, J.ꢀJ. Ho, G. P. A. Yap
and T.ꢀG. Ong, Org. Lett., 2012, 14, 2046. With allylic phosphates:
(f) Y. Makida, H. Ohmiya and M. Sawamura, Angew. Chem. Int. Ed.,
2012, 51, 4122. With Nꢀtosylꢀhydrazones: (g) X. Zaho, G. Wu, Y.
Zhang and J. Wang, J. Am. Chem. Soc., 2011, 133, 3296. (h) T. Yao,
K. Hirano, T. Satoh and M. Miura, Angew. Chem. Int. Ed., 2012, 51,
775. With ethers: (i) T. He, L. Yu, L. Zhang, L. Wang and M. Wang,
Org. Lett., 2011, 13, 5016. Benzoxazoles have been modified by
reaction with functionalized alkyl halogenides: (j) O. Vechorkin, V.
Proust and X. Hu, Angew. Chem. Int. Ed., 2010, 49, 3061. (k) T. Yao,
K. Hirano, T. Satoh and M. Miura, Chem. Eur. J., 2010, 16, 12307.
Y. L. Gol’dfarb, B. P. Fabrichnyĭ and I. F. Shalavina, Tetrahedron,
1961, 18, 21.
will become
a
broadly useable tool for attaching
70
75
80
85
5
functionalized sp3ꢀchains to arenes and heteroarenes.
This research was supported by the PLACEBO (Platform for
Chemical Biology) project as part of the Austrian Genome
Project GENꢀAU funded by the Forschungsförderungsꢀ
10 gesellschaft (FFG) und Bundesministerium für Wissenschaft
und Forschung (BMWF). Lisa Offner, Christian Pichler and
Katharina Plasch are gratefully acknowledged for skillful
assistance in the lab.
Notes and references
15 Institute of Organic Chemistry, Graz University of Technology, Graz
8010, Austria. Fax+43 316 873 32402; Tel: +43 316 873 32400; E-mail:
7
† Electronic Supplementary Information (ESI) available. See
DOI: 10.1039/b000000x/
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11 Azidoꢀthiophene is not stable in the heat and was therefore not
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investigated in this screening.
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