Organic Letters
Letter
Soc. 2010, 132, 10565. (e) Patureau, F. W.; Besset, T.; Glorius, F.
Angew. Chem., Int. Ed. 2011, 50, 1064.
formation of a competing coordinatively saturated complex
15.17
(8) Rhodium: (a) Guimond, N.; Gouliaras, C.; Fagnou, K. J. Am.
Chem. Soc. 2010, 132, 6908. (b) Guimond, N.; Gouliaras, C.; Fagnou,
K. J. Am. Chem. Soc. 2011, 133, 6449. (c) Rakshit, S.; Grohmann, C.;
Besset, T.; Glorius, F. J. Am. Chem. Soc. 2011, 133, 2350. (d) Xu, X.;
Park, C.-M. Angew. Chem., Int. Ed. 2012, 51, 9372. (e) Wang, H.;
Glorius, F. Angew. Chem., Int. Ed. 2012, 51, 7318. (f) Wang, H.;
Grohmann, C.; Nimphius, C.; Glorius, F. J. Am. Chem. Soc. 2012, 134,
19592. (g) Hyster, T. K.; Tomislav, R. Synlett. 2013, 24, 1842.
Ruthenium: (h) Ackermann, L.; Fenner, S. Org. Lett. 2011, 13, 6548.
(i) Li, B.; Feng, H.; Xu, S.; Wang, B. Chem.Eur. J. 2011, 17, 12573−
6548. Transition-metal-free: (j) Manna, S.; Antonchick, A. P. Angew.
Chem., Int. Ed. 2014, 53, 7324.
In summary, a facile method for the preparation of 3,4-
unsubstituted isoquinolones by rhodium-catalyzed C−H
activation/annulation has been established, using vinyl acetate
as a cheap and safe alternative to acetylene. The reaction is
highly efficient and tolerant of a broad range of aromatic
substituents. The regiochemical preferences of arylrhodium
complexes for insertion to electron-rich alkenes has been
probed for the first time. The synthetic utility of vinylic esters
as acetylene equivalents will have broader applicability in C−H
activation chemistry, and further studies will be reported in due
course.
(9) (a) Guimond, N.; Fagnou, K. J. Am. Chem. Soc. 2009, 131, 12050.
(b) Fukutani, T.; Umeda, N.; Hirano, K.; Satoh, T.; Miura, M. Chem.
Commun. 2009, 34, 5141. (c) Wei, X.; Zhao, M.; Du, Z.; Li, X. Org.
Lett. 2011, 13, 4636.
ASSOCIATED CONTENT
■
S
* Supporting Information
(10) (a) Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 132,
9982. (b) Stuart, D. R.; Alsabeh, P.; Kuhn, M.; Fagnou, K. J. Am.
Chem. Soc. 2010, 132, 18326. (c) Stuart, D. R.; Bertrand-Laperle, M.;
Burgess, K. M. N.; Fagnou, K. J. Am. Chem. Soc. 2008, 130, 16474.
(d) Chen, J.; Song, G.; Pan, C.-L.; Li, X. Org. Lett. 2010, 12, 5426.
Experimental procedures, analytical data, and crystallographic
information for all compounds are included. This material is
̌
́
̌ ́ ̌ ́ ̌ ́
kova, L.; Hanikyrova, E.; Skríba, A.; Jasík, J.; Roithova, J. J.
(11) Jasí
AUTHOR INFORMATION
■
Org. Chem. 2012, 77, 2829.
Corresponding Author
(12) For a two-step alternative based upon annulation with
norbornadiene/thermal (170 °C) retro-Diels−Alder reaction, see ref
8b.
(13) (a) Selmeczy, A. D.; Jones, W. D.; Partridge, M. C.; Perutz, R.
N. Organometallics 1994, 13, 522. (b) Li, L.; Brennessel, W. W.; Jones,
W. D. Organometallics 2009, 28, 3492.
Notes
The authors declare no competing financial interest.
(14) Song, Z. J.; Tellers, D. M.; Dormer, P. G.; Zewge, D.; Janey, J.
M.; Nolting, A.; Steinhuebel, D.; Oliver, S.; Devine, P. N.; Tschaen, D.
M. Org. Process Res. Dev. 2014, 18, 423.
(15) Carr, K. J. T.; Davies, D. L.; Macgregor, S. A.; Singh, K.; Villa-
Marcos, B. Chem. Sci. 2014, 5, 2340.
ACKNOWLEDGMENTS
■
We thank AstraZeneca and the EPSRC for financial support.
We also thank Dr. Jonathan Loughrey and Dr. Helena
Shepherd (University of Leeds) for obtaining the crystallo-
graphic data.
(16) Huckins, J. R.; Bercot, E. A.; Thiel, O. R.; Hwang, T.-L.; Bio, M.
M. J. Am. Chem. Soc. 2013, 135, 14492.
(17) Xu, L.; Zhu, Q.; Huang, G.; Cheng, B.; Xia, Y. J. Org. Chem.
2012, 77, 3017.
REFERENCES
■
(1) (a) Matsui, T.; Sugiura, T.; Nakui, H.; Iguch, S.; Shigeoka, S.;
Tukedu, H.; Odagaki, T.; Ushio, Y.; Ohmoto, K.; Iwamani, M.;
Yamazaki, S.; Arai, T.; Kawamura, M. J. Med. Chem. 1992, 35, 3307.
(b) Xie, C.; Veitch, N. C.; Houghton, P. J.; Simmonds, M. S. J.
Phytochemistry 2004, 65, 3041. (c) Sunderland, P. T.; Woon, E. C. Y.;
Dhami, A.; Bergin, A. B.; Mahon, M. F.; Wood, P. J.; Jones, L. A.;
Tully, S. R.; Lloyd, M. D.; Thompson, A. S.; Javaid, H.; Martin, N. M.
B.; Threadgill, M. D. J. Med. Chem. 2011, 54, 2049. (d) Busby, S. A.;
Kumar, N.; Kuruvilla, D. S.; Istrate, M. A.; Conkright, M. A.; Wang, Y.;
Kamenecka, T. M.; Cameron, M. D.; Rous, W. R.; Burris, T. P.;
Griffin, P. R. ACS. Chem. Biol. 2011, 6, 618. (e) Yang, Y.-L.; Chang, F.-
R.; Wu, Y.-C. Tetrahedron Lett. 2003, 44, 319.
(2) Alvarez, M.; Joule, J. A. Sci. Synth. 2005, 15, 839.
(3) Li, S.; Nair, M. G.; Edwards, D. M.; Kisluik, R. L.; Gaumont, Y.;
Dev, I. K.; Duch, D. S.; Humphreys, J.; Smith, G. K.; Ferone, R. J. Med.
Chem. 1991, 34, 2746.
(4) (a) Hirao, K.; Suchiya, R.; Yanu, Y.; Tsue, H. Heterocycles 1996,
42, 415. (b) Briet, N.; Brooks, M. H.; Davenport, R. J.; Galvin, F. C.
A.; Gilbert, P. J.; Mack, S. R.; Sabin, V. Tetrahedron 2002, 58, 5761.
(5) Kiselyov, A. S. Tetrahedron Lett. 1995, 36, 493.
(6) Reviews on Rh(III) catalysed C−H activation: (a) Satoh, T.;
Miura, M. Chem.Eur. J. 2010, 16, 11212. (b) Colby, D. A.; Tsai, A.
S.; Bergman, R. G.; Ellman, J. A. Acc. Chem. Res. 2012, 45, 814.
(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.
(7) (a) Song, G.; Chen, D.; Pan, C.-L.; Crabtree, R. H.; Li, X. J. Org.
Chem. 2010, 75, 7487. (b) Wang, F.; Song, G.; Li, X. Org. Lett. 2010,
12, 5430. (c) Mochida, S.; Umeda, N.; Hirano, K.; Satoh, T.; Miura,
M. Chem. Lett. 2010, 39, 744. (d) Hyster, T. K.; Rovis, T. J. Am. Chem.
D
dx.doi.org/10.1021/ol502095z | Org. Lett. XXXX, XXX, XXX−XXX