Journal of the American Chemical Society
COMMUNICATION
The reaction proceeds selectively at a methyl CÀH bond over a
methylene CÀH bond. The reaction tolerates a variety of func-
tional groups.
(9) Neumann, J. J.; Rakshit, S.; Dr€oge, T.; Glorius, F. Angew. Chem.,
Int. Ed. 2009, 48, 6892.
(10) (a) Desai, L. V.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc.
2004, 126, 9542. (b) Giri, R.; Chen, X.; Yu, J.-Q. Angew. Chem., Int. Ed.
2005, 44, 2112.
’ ASSOCIATED CONTENT
(11) For recent reviews, see: (a) Jia, C.; Kitamura, T.; Fujiwara, Y.
Acc. Chem. Res. 2001, 34, 633. (b) Bhalla, G.; Mironov, O.; Jones, C. J.;
Tenn, W. J., III; Nakamura, S.; Periena, R. A. In Handbook of CÀH
Transformations; Dyker, G., Ed. Wiley-VCH, Weinheim, Germany,
2005; pp 529À542.
S
Supporting Information. Experimental procedures, char-
b
acterization data for all new compounds, and crystallographic
data for 12 (CIF). This material is available free of charge via the
(12) (a) Burk, M. J.; Crabtree, R. H.; Parnell, C. P.; Urlarte, R. J.
Organometallics 1984, 3, 816. (b) Burk, M. J.; Crabtree, R. H. J. Am.
Chem. Soc. 1987, 109, 8025. (c) Nomura, K.; Saito, Y. J. Chem. Soc.,
Chem. Commun. 1988, 161. (d) Sakakura, T.; Sodeyama, T.; Tokunaga,
Y.; Tanaka, M. Chem. Lett. 1988, 263. (e) Maguire, J. A.; Boese, W. T.;
Goldman, A. S. J. Am. Chem. Soc. 1989, 111, 7088. (f) Fujii, T.; Saito, Y.
J. Chem. Soc., Chem. Commun. 1990, 757. (g) Aoki, T.; Crabtree, R. H.
Organometallics 1993, 12, 294. (h) Xu, W.-w.; Rosini, G. P.; Gupta, M.;
Jensen, C. M.; Kaska, W. C.; Krogh-Jespersen, K.; Goldman, A. S. Chem.
Commun. 1997, 2273.
’ AUTHOR INFORMATION
Corresponding Author
’ ACKNOWLEDGMENT
This work was supported in part by a Grant-in-Aid for Scientific
Research on Innovative Areas “Molecular Activation Directed
towardStraightforwardSynthesis”from The Ministry of Education,
Culture, Sports, Science, and Technology.
(13) (a) Chen, H.; Hartwig, J. F. Angew. Chem., Int. Ed. 1999,
38, 3391. (b) Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science
2000, 287, 1995. (c) Kondo, Y.; García-Cuadrado, D.; Hartwig, J. F.;
Boaen, N. K.; Wagner, N. L.; Hillmyer, M. A. J. Am. Chem. Soc. 2002,
124, 1164. (d) Webster, C. E.; Fan, Y.; Hall, M. B.; Kunz, D.; Hartwig,
J. F. J. Am. Chem. Soc. 2003, 125, 858. (e) Lawrence, J. D.; Takahashi, M.;
Bae, C.; Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 15334. (f) Hartwig,
J. F.; Cook, K. S.; Hapke, M.; Incarvito, C. D.; Fan, Y.; Webster, C. E.;
Hall, M. B. J. Am. Chem. Soc. 2005, 127, 2538. (g) Murphy, J. M.;
Lawrence, J. D.; Kawamura, K.; Incarvito, C.; Hartwig, J. F. J. Am. Chem.
Soc. 2006, 128, 13684. Also see: (h) Mkhalid, I. A. I.; Barnard, J. H.;
Marder, T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890.
(14) For a review of C(sp3)ÀH bond activation, see: Crabtree, R. H.
J. Organomet. Chem. 2004, 689, 4083.
(15) Sakakura, T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M.
J. Am. Chem. Soc. 1990, 112, 7221.
(16) Chatani, N.; Asaumi, T.; Ikeda, T.; Yorimitsu, S.; Ishii, Y.;
Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 2000, 122, 12882.
(17) Inoue, S.; Shiota, H.; Fukumoto, Y.; Chatani, N. J. Am. Chem.
Soc. 2009, 131, 6898.
(18) The reaction proceeds via two successive reactions. The first is
Ru-catalyzed CÀH bond carbonylation at the 2-position of pyridine
(see: Moore, E. J.; Pretzer, W. R.; O’Connell, T. J.; Harris, J.; LaBounty,
L.; Chou, L.; Grimmer, S. S. J. Am. Chem. Soc. 1992, 114, 5888). This is
followed by Ru-catalyzed cyclocarbonylation of the resulting pyridinyl
ketone (see:Tobisu, M.; Chatani, N.; Asaumi, T.; Amako, K.; Ie, Y.;
Fukumoto, Y.; Murai, S. J. Am. Chem. Soc. 2000, 122, 12663).
(19) Product 7 would be formed by the hydrolysis of 6, leading to the
production of a 2-aminopyridine that would undergo the hydroamida-
tion with ethylene under the reaction conditions.
(20) The mechanism of H/D exchange at the methylene CÀH bond
in the 2-pyridinylmethyl group is not clear at the present time. For a
recent review of the activation of C(sp3)ÀH bonds adjacent to
nitrogen, see: Campos, K. R. Chem. Soc. Rev. 2007, 36, 1069.
(21) Similar to the case of 2m, H/D exchange at the CH2 group R to
the carbonyl group and at the CH2 group in the 2-pyridinylmethyl group
rather than at the methyl group was also observed in product 2d-(CD3).
(22) Quite recently, photocatalyzed alkane carbonylation was
reported. See: Ryu, I.; Tani, A.; Fukuyama, T.; Ravelli, D.; Fagnoni,
M.; Albini, A. Angew. Chem., Int. Ed. 2011, 50, 1869.
’ REFERENCES
(1) For recent reviews of CÀH bond functionalization, see:
(a) Kakiuchi, F.; Kochi, T. Synthesis 2008, 3013. (b) Colby, D. A.;
Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110, 624. (c) Sehnal, P.;
Taylor, R. J. K.; Fairlamb, I. J. S. Chem. Rev. 2010, 110, 824. (d) Lyons,
T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (e) Xu, L.-M.; Li, B.-J.;
Yang, Z.; Shi, Z.-J. Chem. Soc. Rev. 2010, 39, 712. (f) Ackermann, L.
Chem. Commun. 2010, 46, 4866.
(2) For a recent review of C(sp3)ÀH bond functionalization, see:
Jazzar, R.; Hitce, J.; Renaudat, A.; Sofack-Kreutzer, J.; Baudoin, O. Chem.—
Eur. J. 2010, 16, 2654.
(3) (a) Baudoin, O.; Herrbach, A.; Guꢀeritte, F. Angew. Chem., Int. Ed.
2003, 42, 5736. (b) Hitce, J.; Retailleau, P.; Baudoin, O. Chem.—Eur.
J. 2007, 13, 792. (c) Lafrance, M.; Gorelsky, S. I.; Fagnou, K. J. Am. Chem.
Soc. 2007, 129, 14570. (d) Watanabe, T.; Oishi, S.; Fujii, N.; Ohno, H.
Org. Lett. 2008, 10, 1759. (e) Liꢀegault, B.; Fagnou, K. Organometallics
2008, 27, 4841. (f) Chaumontet, M.; Piccardi, R.; Audic, N.; Hitce, J.;
Peglion, J.-L.; Clot, E.; Baudoin, O. J. Am. Chem. Soc. 2008, 130, 15157.
(g) Chaumontet, M.; Piccardi, R.; Baudoin, O. Angew. Chem., Int. Ed.
2009, 48, 179. (h) Feng, Y.; Wang, Y.; Landgraf, B.; Liu, S.; Chen, G. Org.
Lett. 2010, 12, 3414. (i) Rousseaux, S.; Davi, M.; Sofack-Kreutzer, J.;
Pierre, C.; Kefalidis, C. E.; Clot, E.; Fagnou, K.; Baudoin, O. J. Am. Chem.
Soc. 2010, 132, 10706. (j) Pierre, C.; Baudoin, O. Org. Lett. 2011,
13, 1816.
(4) (a) Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am. Chem. Soc.
2005, 127, 13154. (b) Giri, R.; Maugel, N.; Li, J.-J.; Wang, D.-H.;
Breazzano, S. P.; Saunders, L. B.; Yu, J.-Q. J. Am. Chem. Soc. 2007,
129, 3510. (c) Wang, D.-H.; Wasa, M.; Giri, R.; Yu, J.-Q. J. Am. Chem.
Soc. 2008, 130, 7190. (d) Wasa, M.; Engle, K. M.; Yu, J.-Q. J. Am. Chem.
Soc. 2009, 131, 9886. (e) Shabashov, D.; Daugulis, O. J. Am. Chem. Soc.
2010, 132, 3965. (f) Renaudat, A.; Jean-Gꢀerard, L.; Jazzar, R.; Kefalidis,
C. E.; Clot, E.; Baudoin, O. Angew. Chem., Int. Ed. 2010, 49, 7261.
(5) (a) Dangel, B. D.; Godula, K.; Youn, S. W.; Sezen, B.; Sames, D.
J. Am. Chem. Soc. 2002, 124, 11856. (b) Wasa, M.; Engle, K. M.; Yu, J.-Q.
J. Am. Chem. Soc. 2010, 132, 3680.
(6) (a) Chen, X.; Goodhue, C. E.; Yu, J.-Q. J. Am. Chem. Soc. 2006,
128, 12634. (b) Shi, B.-F.; Maugel, N.; Zhang, Y.-H.; Yu, J.-Q. Angew.
Chem., Int. Ed. 2008, 47, 4882.
(7) (a) Hitce, J.; Baudoin, O. Adv. Synth. Catal. 2007, 349, 2054. (b)
Johnson, J. A.; Li, N.; Sames, D. J. Am. Chem. Soc. 2002, 124, 6900. (c) Giri,
R.; Maugel, N.; Foxman, B. M.; Yu, J.-Q. Organometallics 2008, 27, 1667.
(8) During the preparation of this manuscript, a similar carbonylation
of unactivated C(sp3)ÀH bonds catalyzed by Pd(II) was reported. See:
Yoo, E. J.; Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 17378.
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dx.doi.org/10.1021/ja2001709 |J. Am. Chem. Soc. 2011, 133, 8070–8073