Organic Letters
Letter
685−686. (e) Genet, C.; Canipa, S. J.; O’Brien, P.; Taylor, S. J. Am.
Chem. Soc. 2006, 128, 9336−9337. (f) Steffen, P.; Unkelbach, C.;
Christmann, M.; Hiller, W.; Strohmann, C. Angew. Chem., Int. Ed.
2013, 52, 9836−9840.
absolute configuration of 2j was assigned as Sp by X-ray
crystallographic analysis.19
In conclusion, we have developed a concise way to synthesize
quinolin-2(1H)-ones equipped with a planar chiral ferrocene
moiety in an enantioselective manner, providing an example of
asymmetric synthesis of ferrocene derivatives fused with
nitrogen-containing heterocycles via enantioselective C−H
activation.
(6) (a) Marquarding, D.; Klusacek, H.; Gokel, G.; Hoffmann, P.; Ugi,
I. J. Am. Chem. Soc. 1970, 92, 5389−5393. (b) Riant, O.; Samuel, O.;
̀
Kagan, H. B. J. Am. Chem. Soc. 1993, 115, 5835−5836. (c) Rebiere, F.;
Riant, O.; Ricard, L.; Kagan, H. B. Angew. Chem., Int. Ed. 1993, 32,
568−570. (d) Enders, D.; Peters, R.; Lochtman, R.; Raabe, G. Angew.
Chem., Int. Ed. 1999, 38, 2421−2423. (e) Bolm, C.; Kesselgruber, M.;
ASSOCIATED CONTENT
* Supporting Information
Muniz, K.; Raabe, G. Organometallics 2000, 19, 1648−1651.
̃
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́
(f) Voituriez, A.; Panossian, A.; Fleury-Bregeot, N.; Retailleau, P.;
S
Marinetti, A. J. Am. Chem. Soc. 2008, 130, 14030−14031.
(7) (a) Siegel, S.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1997, 36,
2456−2458. (b) Bueno, A.; Rosol, M.; Garcia, J.; Moyano, A. Adv.
Synth. Catal. 2006, 348, 2590−2596. (c) Ogasawara, M.; Watanabe, S.;
Fan, L.; Nakajima, K.; Takahashi, T. Organometallics 2006, 25, 5201−
5203. (d) Duan, W.-L.; Imazaki, Y.; Shintani, R.; Hayashi, T.
Tetrahedron 2007, 63, 8529−8536. (e) Patti, A.; Pedotti, S.
Tetrahedron: Asymmetry 2010, 21, 2631−2637.
Experimental procedures, spectroscopic data for new com-
pounds, and details of X-ray crystallographic analysis for 2j.
This material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Authors
■
(8) For reviews on enantioselective C−H activation, see: (a) Wencel-
Delord, J.; Colobert, F. Chem.Eur. J. 2013, 19, 14010−14017.
(b) Zheng, C.; You, S.-L. RSC Adv. 2014, 4, 6173−6214.
(9) (a) Gao, D.-W.; Shi, Y.-C.; Gu, Q.; Zhao, Z.-L.; You, S.-L. J. Am.
Chem. Soc. 2013, 135, 86−89. (b) Shi, Y.-C.; Yang, R.-F.; Gao, D.-W.;
You, S.-L. Beilstein J. Org. Chem. 2013, 9, 1891−1896. (c) Pi, C.; Li, Y.;
Cui, X.; Zhang, H.; Han, Y.; Wu, Y. Chem. Sci. 2013, 4, 2675−2679.
(d) For a pioneering work on Pd-catalyzed diastereoselective C−H
activation of ferrocene, see: Xia, J.-B.; You, S.-L. Organometallics 2007,
26, 4869−4871.
(10) Shibata, T.; Shizuno, T. Angew. Chem., Int. Ed. 2014, 53, 5410−
5413.
(11) (a) Deng, R.; Huang, Y.; Ma, X.; Li, G.; Zhu, R.; Wang, B.;
Kang, Y.-B.; Gu, Z. J. Am. Chem. Soc. 2014, 136, 4472−4475. (b) Gao,
D.-W.; Yin, Q.; Gu, Q.; You, S.-L. J. Am. Chem. Soc. 2014, 136, 4841−
4844.
Author Contributions
§These authors contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21202095) and the Program for Science
& Technology Innovation Talents in Universities of Henan
Province (14HASTIT016).
(12) Sreeshailam, A.; Dayaker, G.; Ramana, D. V.; Chevallier, F.;
Roisnel, T.; Komagawa, S.; Takita, R.; Uchiyama, M.; Krishna, P. R.;
Mongin, F. R. RSC Adv. 2012, 2, 7030−7032.
(13) (a) Ruble, J. C.; Fu, G. C. J. Org. Chem. 1996, 61, 7230−7231.
(b) Hu, B.; Meng, M.; Wang, Z.; Du, W.; Fossey, J. S.; Hu, X.; Deng,
W.-P. J. Am. Chem. Soc. 2010, 132, 17041−17044.
REFERENCES
■
(1) (a) Hayashi, T.; Kumada, M. Acc. Chem. Res. 1982, 15, 395−401.
(b) Halterman, R. L. Chem. Rev. 1992, 92, 965−994. (c) Richards, C.
J.; Locke, A. J. Tetrahedron: Asymmetry 1998, 9, 2377−2407. (d) Blaser,
H.-U.; Brieden, W.; Pugin, B.; Spindler, F.; Studer, M.; Togni, A. Top.
Catal. 2002, 19, 3−16. (e) Dai, L.-X.; Tu, T.; You, S.-L.; Deng, W.-P.;
Hou, X.-L. Acc. Chem. Res. 2003, 36, 659−667. (f) Colacot, T. J. Chem.
(14) During preparation of this manuscript, an analogous palladium-
catalyzed intramolecular C−H arylation reaction producing planar
chiral ferrocenes with moderate enantioselectivity (up to 67% ee) has
appeared: Ma, X.; Gu, Z. RSC Adv. 2014, 4, 36241−36244.
(15) The reaction failed when other bases including K2CO3, Na2CO3,
́
Rev. 2003, 103, 3101−3118. (g) Arrayas, R. G.; Adrio, J.; Carretero, J.
C. Angew. Chem., Int. Ed. 2006, 45, 7674−7715. (h) Fu, G. C. Acc.
Chem. Res. 2006, 39, 853−860. (i) Arae, S.; Ogasawara, M. J. Synth.
Org. Chem., Jpn. 2012, 70, 593−605. (j) Dai, L.-X., Hou, X.-L., Eds.
Chiral Ferrocenes in Asymmetric Catalysis; Wiley-VCH: Weinheim,
2010.
t
NaHCO3, BuONa, and Et3N were employed instead of Cs2CO3. No
reaction took place in the absence of pivalic acid.
(16) The pivalate ligand would facilitate C−H activation via
concerted metalation−deprotonation mechanism: (a) Garcia-
Cuadrado, D.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M. J. Am.
Chem. Soc. 2006, 128, 1066−1067. (b) Lafrance, M.; Fagnou, K. J. Am.
Chem. Soc. 2006, 128, 16496−16497.
(17) It is reported that an N-unsubstituted quinolinone-fused
ferrocene racemizes in solution (ref 12). However, the erosion of
the enantiomeric excess of N-butyl derivative 2e was not observed in
toluene even at refluxing temperature.
(18) Low enantioselectivities were observed when pyridine-
containing substrates were subjected to the optimized reaction
conditions. See the Supporting Information for details.
(19) CCDC1002966 (2j) contains the supplementary crystallo-
graphic data for this paper.
(2) (a) Fabre, B. Acc. Chem. Res. 2010, 43, 1509−1518. (b) Tarafder,
K.; Surendranath, Y.; Olshansky, J. H.; Alivisatos, A. P.; Wang, L. J.
Am. Chem. Soc. 2014, 136, 5121−5131. (c) Tropiano, M.; Kilah, N. L.;
Morten, M.; Rahman, H.; Davis, J. J.; Beer, P. D.; Faulkner, S. J. Am.
Chem. Soc. 2011, 133, 11847−11849.
(3) (a) van Staveren, D. R.; Metzler-Nolte, N. Chem. Rev. 2004, 104,
5931−5986. (b) Fouda, M. F. R.; Abd-Elzaher, M. M.; Abdelsamaia, R.
A.; Labib, A. A. Appl. Organometal. Chem. 2007, 21, 613−625.
(c) Hartinger, C. G.; Dyson, P. J. Chem. Soc. Rev. 2009, 38, 391−401.
(d) Gasser, G.; Ott, I.; Metzler-Nolte, N. J. Med. Chem. 2011, 54, 3−
25. (e) Braga, S. S.; Silva, A. M. S. Organometallics 2013, 32, 5626−
5639.
(4) A recent review on selective synthesis of planar-chiral ferrocenes:
Schaarschmidt, D.; Lang, H. Organometallics 2013, 32, 5668−5704.
(5) (a) Price, D.; Simpkins, N. S. Tetrahedron Lett. 1995, 36, 6135−
6136. (b) Dayaker, G.; Tilly, D.; Chevallier, F.; Hilmersson, G.; Gros,
P. C.; Mongin, F. Eur. J. Org. Chem. 2012, 6051−6057.
(c) Nishibayashi, Y.; Arikawa, Y.; Ohe, K.; Uemura, S. J. Org. Chem.
1996, 61, 1172−1174. (d) Tsukazaki, M.; Tinkl, M.; Roglans, A.;
Chapell, B. J.; Taylor, N. J.; Snieckus, V. J. Am. Chem. Soc. 1996, 118,
C
dx.doi.org/10.1021/ol502520b | Org. Lett. XXXX, XXX, XXX−XXX