ChemComm
Communication
2010, 16, 11212; (i) L. Ackermann, R. Vicente and A. Kapdi, Angew.
Chem., Int. Ed., 2009, 48, 9792.
4 Representative references: (a) A. R. Dick, K. L. Hull and M. S. Sanford,
J. Am. Chem. Soc., 2004, 126, 2300; (b) S. R. Whitfield and
M. S. Sanford, J. Am. Chem. Soc., 2007, 129, 15142; (c) S. R. Neufeldt
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5 (a) R. Giri, X. Chen and J.-Q. Yu, Angew. Chem., Int. Ed., 2005,
44, 2112; (b) J.-J. Li, T.-S. Mei and J.-Q. Yu, Angew. Chem., Int. Ed.,
2008, 47, 6452; (c) T.-S. Mei, R. Giri, N. Maugel and J.-Q. Yu, Angew.
Chem., Int. Ed., 2008, 47, 5215; (d) X.-C. Wang, Y. Hu, S. Bonacorsi,
Y. Hong, R. Burrell and J.-Q. Yu, J. Am. Chem. Soc., 2013, 135, 10326;
and references cited therein.
6 Representative examples: (a) X. Wan, Z. Ma, B. Li, K. Zhang, S. Cao,
S. Zhang and Z. Shi, J. Am. Chem. Soc., 2006, 128, 7416; (b) X. Zhao,
Scheme 5 C–H functionalization with labelled compound [D]1-4.
´
E. Dimitrijevic and V. M. Dong, J. Am. Chem. Soc., 2009, 131, 3466;
(c) F. Kakiuchi, T. Kochi, H. Mutsutani, N. Kobayashi, S. Urano, M. Sato,
S. Nishiyama and T. Tanabe, J. Am. Chem. Soc., 2009, 131, 11310;
(d) R. B. Bedford, M. F. Haddow, C. J. Mitchell and R. L. Webster, Angew.
Chem., Int. Ed., 2011, 50, 5524; (e) X. Sun, G. Shan, Y. Sun and Y. Rao,
Angew. Chem., Int. Ed., 2013, 52, 4440; and references cited therein.
7 For rare examples of copper-mediated processes, see: (a) W. Wang,
C. Pan, F. Chen and J. Chen, Chem. Commun., 2011, 47, 3978;
(b) S. Mo, Y. Zhu and Z. Shen, Org. Biomol. Chem., 2013, 11, 2756.
¨
8 (a) N. Schroder, J. Wencel-Delord and F. Glorius, J. Am. Chem. Soc.,
¨
2012, 134, 8298; see also: (b) N. Kuhl, N. Schroder and F. Glorius,
Scheme 6 Kinetic isotope effect studies.
Org. Lett., 2013, 15, 3860.
9 In September 2013, the prices of platinum, rhodium, gold, iridium,
palladium and ruthenium were 1482, 1015, 1363, 800, 701 and 80
metalpricesusdollars.html.
1a and [D]5-1a did not reveal a significant kinetic isotope effect
(KIE, kH/kD E 1.0),21 hence being indicative of the C–H cleavage
not to be kinetically relevant (Scheme 6).
In summary, we have reported on the first ruthenium-catalyzed
ortho-selective C–H halogenations on arenes through C–H activa-
tion. Thus, a catalytic system comprising of [Ru3(CO)12] and
AgO2C(1-Ad) allowed site-selective brominations and iodinations
on amides with ample scope and excellent functional group
tolerance. Preliminary mechanistic studies provided evidence for
a reversible C–H metalation event.
10 Selected reviews: (a) V. S. Thirunavukkarasu, S. I. Kozhushkov and
L. Ackermann, Chem. Commun., 2014, 50, 29; (b) L. Ackermann, Acc.
Chem. Res., 2013, DOI: 10.1021/ar3002798; (c) S. I. Kozhushkov and
L. Ackermann, Chem. Sci., 2013, 4, 886; (d) P. B. Arockiam,
C. Bruneau and P. H. Dixneuf, Chem. Rev., 2012, 112, 5879;
(e) L. Ackermann and R. Vicente, Top. Curr. Chem., 2010, 292, 211.
11 Recent examples of oxidative C–C formations: (a) J. D. Dooley,
C. S. Reddy and H. W. Lam, J. Am. Chem. Soc., 2013, 135, 10829;
(b) L. Wang and L. Ackermann, Org. Lett., 2013, 15, 176; (c) P. Villuendas
and E. P. Urriolabeitia, J. Org. Chem., 2013, 78, 5254; (d) P. Kishor and
M. Jeganmohan, Org. Lett., 2012, 14, 1134; (e) B. Li, J. Ma, N. Wang,
H. Feng, S. Xu and B. Wang, Org. Lett., 2012, 14, 736; ( f ) L. Ackermann,
L. Wang and A. V. Lygin, Chem. Sci., 2012, 3, 177; (g) Y. Hashimoto,
T. Ueyama, T. Fukutani, K. Hirano, T. Satoh and M. Miura, Chem. Lett.,
2011, 1165; (h) L. Ackermann and S. Fenner, Org. Lett., 2011, 13, 6548;
(i) L. Ackermann, A. V. Lygin and N. Hofmann, Angew. Chem., Int. Ed.,
2011, 50, 6379.
Support from the European Research Council under the Euro-
pean Community’s Seventh Framework Program (FP7 2007–2013)/
ERC Grant agreement no. 307535 and the Chinese Scholarship
Council (fellowship to L.W.) is gratefully acknowledged.
12 Selected examples of oxidative C–O formations: (a) W. Liu and
L. Ackermann, Org. Lett., 2013, 15, 3484; (b) F. Yang and L. Ackermann,
Org. Lett., 2013, 15, 718; (c) V. S. Thirunavukkarasu and L. Ackermann,
Org. Lett., 2012, 14, 6206; (d) V. S. Thirunavukkarasu, J. Hubrich and
L. Ackermann, Org. Lett., 2012, 14, 4210; (e) Y. Yang, Y. Lin and Y. Rao,
Org. Lett., 2012, 14, 2874.
Notes and references
1 Selected reviews: (a) S. Johansson, C. C. Carin, M. O. Kitching,
T. J. Colacot and V. Snieckus, Angew. Chem., Int. Ed., 2012, 51, 5062;
(b) T. A. Lansdell, N. M. Hewlett, A. P. Skoumbourdis, M. D. Fodor,
I. B. Seiple, S. Su, P. S. Baran, K. S. Feldman and J. J. Tepe, J. Nat. 13 Recent examples of C–N formations: (a) V. S. Thirunavukkarasu,
Prod., 2012, 75, 980; (c) G. Evano, N. Blanchard and M. Toumi, Chem.
Rev., 2008, 108, 3054; (d) K. C. Nicolaou, P. G. Bulger and D. Sarlah,
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V. A. Vu, Angew. Chem., Int. Ed., 2003, 42, 4302; and cited references.
K. Raghuvanshi and L. Ackermann, Org. Lett., 2013, 15, 3286;
(b) M. Bhanuchandra, M. R. Yadav, R. K. Rit, M. R. Kuram and
A. K. Sahoo, Chem. Commun., 2013, 49, 5225; (c) M.-L. Louillat and
F. W. Patureau, Org. Lett., 2013, 15, 164; (d) J. Hu, S. Chen, Y. Sun,
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2 (a) Y. L. Janin, Chem. Rev., 2012, 112, 3924; (b) S. D. Roughley and 14 An intramolecular halogenation of selected ortho-methylbenzohydro-
A. M. Jordan, J. Med. Chem., 2011, 54, 3451; (c) A. Podgorsek, M. Zupan
and J. Iskra, Angew. Chem., Int. Ed., 2009, 48, 8424; (d) E. J.-G. Anctil and
ximoyl halides: R. K. Chinnagolla, S. Pimparkar and M. Jeganmohan,
Chem. Commun., 2013, 49, 3146.
V. Snieckus, in Metal-Catalyzed Cross-Coupling Reactions, ed. A. de Meijere 15 L. Ackermann, Chem. Rev., 2011, 111, 1315.
and F. Diederich, Wiley-VCH, Weinheim, 2004, p. 761; (e) E. B. 16 ortho-Hydroxylated products were only observed during the early
Merkushev, Synthesis, 1988, 923; and cited references.
3 Recent selected reviews on C–H activation: (a) K. M. Engle and J.-Q. Yu,
J. Org. Chem., 2013, 78, 8927; (b) X. Kuhl, M. N. Hopkinson, J. Wencel-
optimization studies, and C–O bond forming reactions did not
occur when using AgO2C(1-Ad) as the additive. Primary and second-
ary benzamides provided thus far only unsatisfactory results.
Delord and F. Glorius, Angew. Chem., Int. Ed., 2012, 51, 10236; 17 For detailed information, see the ESI†.
(c) C. S. Yeung and V. M. Dong, Chem. Rev., 2011, 111, 1215; 18 A review: D. Balcells, E. Clot and O. Eisenstein, Chem. Rev., 2010, 110, 749.
(d) S. H. Cho, J. Y. Kim, J. Kwak and S. Chang, Chem. Soc. Rev., 2011, 19 Under the optimized reaction conditions the mass balance is
40, 5068; (e) D. A. Colby, R. G. Bergman and J. A. Ellman, Chem. Rev.,
2010, 110, 624; ( f ) T. W. Lyons and M. S. Sanford, Chem. Rev., 2010,
accounted for by the unreacted starting materials as well as the
second regioisomers in case of meta-substituted substrates 1.
110, 1147; (g) X. Chen, K. M. Engle, D.-H. Wang and J.-Q. Yu, Angew. 20 T. C. Wabnitz, J.-Q. Yu and J. B. Spencer, Chem.–Eur. J., 2004, 10, 484.
Chem., Int. Ed., 2009, 48, 5094; (h) T. Satoh and M. Miura, Chem.–Eur. J., 21 E. M. Simmons and J. F. Hartwig, Angew. Chem., Int. Ed., 2012, 51, 3066.
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