10.1002/anie.201704922
Angewandte Chemie International Edition
COMMUNICATION
H.-C. Guo, J.-A. Ma, Angew. Chem. Int. Ed. 2006, 45, 354-366. j) T.
Miura, M. Murakami, Chem. Commun. 2007, 217–224. k) S. W. Youn,
Eur. J. Org. Chem. 2009, 2597–2605.
lacking the olefin moiety, to the standard reaction conditions led
to the direct reduction of the carbon-halogen bond, suggesting
that the direct oxidative addition pathway (Pathway II or III) is
possible (Scheme 3b). Similarly, upon subjecting the substrate
1a’’, lacking the carbon-bromine bond, to the standard reaction
conditions, reduction of the olefin was also observed in 50% yield
and 4% ee (Scheme 3c). These results support the benefit of a
synergistic interaction of both functional groups, as neither goes
to full completion, in contrast to the result obtained when both the
halide and the olefin are present. Overall, although the exact
sequence of mechanistic events remains unclear, the
enantiodetermining step may involve the formation of III or
reductive elimination.
[6]
a) S. J. Taylor, M. O. Duffey, J. P. Morken, J. Am. Chem. Soc. 2000, 122,
4528-4529. b) C.-X. Zhao, J. Bass, J. P. Morken, Org. Lett. 2001, 3,
2839-2842. c) K. Yoshida, M. Ogasawara, T. Hayashi J. Am. Chem. Soc.
2002, 124, 10984-10985. d) A. E. Russell, N. O. Fuller, S. J. Taylor, P.
Aurriset, J. P. Morken, Org. Lett. 2004, 6, 2309-2312.
[7]
[8]
[9]
Y. J. Jang, H. Yoon, M. Lautens, Org. Lett. 2015, 17, 3895-3897.
R. Shintani, T. Yamagami, T. Hayashi, Org. Lett. 2006, 8, 4799-4801.
For
a
review on recent developments of rhodium-catalyzed
hydrofunctionalization reaction, please see: P. Koschker, B. Breit, Acc.
Chem. Res. 2016, 49, 1524-1536.
[10] a) A. Canas-Rodriguez, P. R. Leeming, J. Med. Chem. 1972, 15, 762-
770. b) M. K. Uddin, S. G. Reignier, T. Coulter, C. Montalbett, C. Grånäs,
S. Butcher, C. Krog-Jensen, J. Felding, Bioorg. Med. Chem. Lett. 2007,
17, 2854-2857. c) B. Volk, J. Barkóczy, E. Hegedus, S. Udvari, I. Gacsály,
T. Mezei, K. Pallagi, H. Kompagne, G. Lévay, A. Egyed, L. G. Hársing
Jr., M. Spedding, G. Simig, J. Med. Chem. 2008, 51, 2522-2532. d) B.
Volk, I. Gacsály, K. Pallagi, L. Poszávácz, I. Gyönös, E. Szabó, T. Bakó,
M. Spedding, G. Simig, G. Szénási, J. Med. Chem. 2011, 54, 6657-6669.
e) M. M. Herth, V. L. Andersen, H . D. Hansen, N. Stroth, B. Volk, S.
Lehel, A. Dyssegaard, A. Ettrup, P. Svenningsson, G. M. Knudsen, J. L.
Kristensen, J. Med. Chem. 2015, 58, 3631–3636.
In conclusion, we have successfully demonstrated the
rhodium-catalyzed enantioselective intramolecular hydroarylation
reaction. This operationally simple methodology provides rapid
access to 3,3-disubstitued oxindoles with good to excellent
enantiocontrol, and further studies are underway for a better
understanding of the mechanism.
Acknowledgements ((optional))
[11] a) T. M. Seidel, Y. -J. Jia, G. Bnernardinelli, E. P. Kϋndig, Angew. Chem.
Int. Ed. 2007, 46, 8484-8487. b) A. M. Taylor, R. A. Altman, S. L.
Buchwald, J. Am. Chem. Soc. 2009, 131, 9900-9901. c) S. Wurtz, C.
Lohre, K. Bergander, F. Glorius, J. Am. Chem. Soc. 2009, 131, 8344-
8345. d) D. Katayev, Y. -J. Jia, A. K. Sharma, D. Banerjee, R. B. Sunoj,
E. P. Kϋndig, Chem. Eur. J. 2013, 19, 11916-11927.
We thank the University of Toronto, NSERC and Alphora
Research Inc. for their support of our project. We would also like
to thank Dr. D. Petrone (ETH Zurich), Dr. C. M. Le (University of
California, Berkeley), H. Yoon, Dr. I. Franzoni, Dr. M. Wegmann
(University of Toronto) for their suggestions and discussions
throughout the project. Special thanks to the NMR staff, Dr. J.
Sheng and Dr. D. Burns (University of Toronto) for their help with
the NMR studies. Dr. Alan Lough is thanked for his contributions
with X-ray crystallography and Dr. Matthew W. Forbes (University
of Toronto) is thanked for his help with mass spectroscopy. We
gratefully acknowledge Solvias for their generous donation of
Josiphos ligands.
[12] For reviews on the synthesis of 3,3-disubstituted oxindoles, please see:
a) F. Zhou, Y. -L. Liu, J. Zhou, Adv. Synth. Catal. 2010, 352, 1381-1407.
b) Z. -Y. Cao, Y. -H. Wang, X. -P. Zeng, J. Zhou, Tetrahedron. Lett. 2014,
55, 2571-2584.
[13] a) Y. Harada, J. Nakanishi, H. Fujihara, M. Tobisu, Y. Fukumoto, N.
Chatani, J. Am. Chem. Soc. 2007, 129, 5766. b) T. Morimoto, K.
Yamasaki, A. Hirano, K. Tsutsumi, N. Kagawa, K. Kakiuchi, Y. Harada,
Y. Fukumoto, N. Chatani, T. Nishioka, Org. Lett. 2009, 11, 1777-1780. c)
M. Fujioka, T. Morimoto, T. Tsumagari, H. Tanimoto, Y. Nishiyama, K.
Kakiuchi, J. Org. Chem. 2012, 77, 2911-2923. d) R. Shintani, R. Lino, K.
Nozaki, J. Am. Chem. Soc. 2016, 138, 3635-3638. e) K. Takahashi, S.
Ito, R. Shintani, K. Nozaki, Chem. Sci. 2017, 8, 101-107.
Keywords: Rhodium Catalysis • 3,3-Disubstituted Oxindole •
Enantioselective Cyclization • Hydroarylation • Reductive
Arylation
[14] W. C. Kaska, S. Nemeh, A. Shirazi, S. Potuznik, Organometallics, 1988,
7, 13-15.
[15] No reduction of the aryl-bromide bond is observed in the reaction
Scheme 3b in the absence of the rhodium catalyst.
[1]
[2]
M. Sakai, H. Hayashi, N. Miyaura, Organometallics 1997, 16, 4229-4231.
T. Yoshiaki, M. Ogasawara, T. Hayashi, J. Am. Chem. Soc. 1998, 120,
5579-5580.
[3]
a) T. Hayashi, M. Takahashi, Y. Takaya, M. Ogasawara, J. Am. Chem.
Soc. 2002, 124, 5052–5058. For comprehensive reviews on rhodium-
catalyzed 1,4-conjugate additions and its related processes please see:
b) T. Hayashi, Synlett 2001, 879-887. c) K. Fagnou, M. Lautens, Chem.
Rev. 2003, 103, 169-196. d) T. Hayashi, K. Yamasaki, Chem. Rev. 2003,
103, 2829-2844. e) J. D. Hargrave, J. C. Allen, C. G. Frost, Chem. Asian
J. 2010, 5, 386-396. f) H. J. Edwards, J. D. Hargrave, S. D. Penrose, C.
G. Frost, Chem. Soc. Rev. 2010, 39, 2093-2105.
[4]
[5]
G. Berthon, T. Hayashi in Catalytic Asymmetric Conjugate Reactions, Ch.
1 (Eds.: A. Córdova), Wiley-VCH, Weinheim, 2010, pp.1-70.
a) M. Lautens, J. Mancuso, J. Org. Chem. 2004, 69, 3478-3487. b) M.
Lautens, T. Marquardt, J. Org. Chem. 2004, 69, 4607-4614. c) R.
Shintani, A. Tsurusaki, K. Okamoto, T. Hayashi, Angew. Chem. Int. Ed.
2005, 44, 3909 –3912. d) R. Shintani, K. Okamoto, Y. Otomaru, K.
Ueyama, T. Hayashi, J. Am. Chem. Soc. 2005, 127, 54–55. e) T. Miura,
T. Harumashi, M. Murakami, Org. Lett. 2007, 9, 741-743. f) C. Navarro,
A. G. Csákÿ, Org. Lett. 2008, 10, 217-219. g) S. W. Youn, J.-H. Song,
D.-I. Jung, J. Org. Chem. 2008, 73, 5658–5661. h) N.-W. Tseng, M.
Lautens, J. Org. Chem. 2009, 74, 1809–1811. For comprehensive
reviews on transition-metal-catalyzed tandem processes, please see: i)
This article is protected by copyright. All rights reserved.