Organic Letters
Letter
groups, have also been reported: (a) Zhu, C.; Falck, J. R. Chem. Commun.
2012, 48, 1674. (b) Zhu, C.; Falck, J. R. Tetrahedron 2012, 68, 9192.
(c) Cui, S.; Zhang, Y.; Wang, D.; Wu, Q. Chem. Sci. 2013, 4, 3912.
(d) Lam, H.-W.; Man, K.-Y.; Chan, W.-W.; Zhou, Z.; Yu, W.-Y. Org.
Biomol. Chem. 2014, 12, 4112. (e) Ye, B.; Cramer, N. Angew. Chem., Int.
Ed. 2014, 53, 7896. (f) Shi, J.; Zhou, J.; Yan, Y.; Jia, J.; Liu, X.; Song, H.;
Xu, H. E.; Yi, W. Chem. Commun. 2015, 51, 668. (g) Yu, S.; Liu, S.; Lan,
Y.; Wan, B.; Li, X. J. Am. Chem. Soc. 2015, 137, 1623. (h) Li, X. G.; Sun,
M.; Liu, K.; Jin, Q.; Liu, P. N. Chem. Commun. 2015, 51, 2380. (i) Wang,
H.-L.; Shang, M.; Sun, S.-Z.; Zhou, Z.-L.; Laforteza, B. N.; Dai, H.-X.;
Yu, J.-Q. Org. Lett. 2015, 17, 1228.
(8) Recently, cyclic allyl carbonates, which have a CC bond at a
different position, have been used as substrates for rhodium-catalyzed
C−H functionalization to give allyl alcohols and N-heterocycles:
(a) Zhang, S.-S.; Wu, J.-Q.; Lao, Y.-X.; Liu, X.-G.; Liu, Y.; Lv, W.-X.; Tan,
D.-H.; Zeng, Y.-F.; Wang, H. Org. Lett. 2014, 16, 6412. (b) Zhang, S.-S.;
Wu, J.-Q.; Liu, X.; Wang, H. ACS Catal. 2015, 5, 210.
(9) (a) Matsuura, Y.; Tamura, M.; Kochi, T.; Sato, M.; Chatani, N.;
Kakiuchi, F. J. Am. Chem. Soc. 2007, 129, 9858. (b) Ogiwara, Y.; Tamura,
M.; Kochi, T.; Matsuura, Y.; Chatani, N.; Kakiuchi, F. Organometallics
2014, 33, 402. (c) Ogiwara, Y.; Kochi, T.; Kakiuchi, F. Chem. Lett. 2014,
43, 667.
(10) Metal-catalyzed C−C bond formation using cyclic alkenyl
carbonates: (a) Ohe, K.; Matsuda, H.; Ishihara, T.; Ogoshi, S.;
Chatani, N.; Murai, S. J. Org. Chem. 1993, 58, 1173. (b) Toullec, P.;
Martin, A. C.; Gio-Batta, M.; Bruneau, C.; Dixneuf, P. H. Tetrahedron
Lett. 2000, 41, 5527. (c) Bigovic, M.; Skaro, S.; Maslak, V.; Saicic, R. N.
Tetrahedron Lett. 2013, 54, 6624.
Figure 1. Possible mechanism of the rhodium-catalyzed α-acylalkylation
of arenes with cyclic alkenyl carbonates.
compounds bearing a variety of substituents including both
electron-donating and withdrawing groups and various cyclic
alkenyl carbonates can be applied for this reaction. One-pot
formation of isocoumarins by C−H functionalization/cyclization
was also achieved.
ASSOCIATED CONTENT
* Supporting Information
■
S
(11) (a) Fournier, J.; Bruneau, C.; Dixneuf, P. H. Tetrahedron Lett.
1989, 30, 3981. (b) Buzas, A.; Gagosz, F. Org. Lett. 2006, 8, 515.
(c) Buzas, A. K.; Istrate, F. M.; Gagosz, F. Tetrahedron 2009, 65, 1889.
(12) Reviews on C−H functionalization using Cp*Rh catalysts:
(a) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110,
624. (b) Satoh, T.; Miura, M. Chem. - Eur. J. 2010, 16, 11212.
(c) Patureau, F. W.; Wencel-Delord, J.; Glorius, F. Aldrichimica Acta
2012, 45, 31. (d) Song, G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41,
3651. (e) Zhang, X.-S.; Chen, K.; Shi, Z.-J. Chem. Sci. 2014, 5, 2146.
(13) Reduction of the catalyst loadings to 2.5 mol % of [Cp*RhCl2]2
and 10 mol % of AgBF4 under the reaction conditions decreased the
yield to 49%.
The Supporting Information is available free of charge on the
Full experimental details and characterization data (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
(14) Directed C−H functionalization at the more sterically congested
ortho position of benzamide derivatives having an ether oxygen atom at
the meta position has been reported: (a) Wang, L.; Ackermann, L. Chem.
ACKNOWLEDGMENTS
■
This work was supported, in part, by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports,
Science and Technology, Japan, JST, ACT-C, and the Asahi
Glass Foundation.
Commun. 2014, 50, 1083. (b) Schroder, N.; Wencel-Delord, J.; Glorius,
̈
F. J. Am. Chem. Soc. 2012, 134, 8298.
(15) Transition-metal-mediated or -catalyzed formation of 3-
substituted isocoumarins without a substituent at the 4-position via
C−H bond cleavage: (a) Larock, R. C.; Varaprath, S.; Lau, H. H.;
Fellows, C. A. J. Am. Chem. Soc. 1984, 106, 5274. (b) Miura, M.; Tsuda,
T.; Satoh, T.; Pivsa-Art, S.; Nomura, M. J. Org. Chem. 1998, 63, 5211.
(c) Nandi, D.; Ghosh, D.; Chen, S.-J.; Kuo, B.-C.; Wang, N. M.; Lee, H.
M. J. Org. Chem. 2013, 78, 3445.
(16) Many examples of transition-metal-catalyzed formation of 3,4-
disubstituted isocoumarins via C−H bond cleavage have been reported.
For a pioneering study, see: Ueura, K.; Satoh, T.; Miura, M. Org. Lett.
2007, 9, 1407.
(17) Kurume, A.; Kamata, Y.; Yamashita, M.; Wang, Q.; Matsuda, H.;
Yoshikawa, M.; Kawasaki, I.; Ohta, S. Chem. Pharm. Bull. 2008, 56, 1264.
(18) The highly electrophilic nature of dicationic Rh(III) species A
may prevent the catalyst from reacting with the cyclic alkenyl carbonate
and forming an oxatrimethylenemethane complex. For the formation of
oxatrimethylenemethane palladium complexes from cyclic alkenyl
carbonates, see: Ohe, K.; Matsuda, H.; Ishihara, T.; Ogoshi, S.;
Chatani, N.; Murai, S. J. Org. Chem. 1993, 58, 1173.
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D
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