Journal of the American Chemical Society
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FIGURE 2. 3D structures and schematic representation models of
TSrsyn-R and TSssyn-S (3,3’-substituents of BINOL-phosphoric
acid: ball model, substrates: tube model). Relative energy differ-
ences (kcal/mol) are shown in parentheses.
In conclusion, we have developed a highly efficient kinetic res-
olution of indoline derivatives by the chiral phosphoric acid cata-
lyzed asymmetric transfer hydrogenation of indoline to imine. The
kinetic resolution allows the synthesis of 2-substituted and 2,3-
disubstituted indolines in high yields with excellent enantioselec-
tivities. The method features a mild oxidative kinetic resolution
using the hydrogen transfer reaction. Further investigation of the
mechanistic insights and the applications to the synthesis of more
complex molecules is under way in our laboratory.
(8)The asymmetric synthesis of chiral indolines have been also
achieved by following methods. Asymmetric hydrogenation, see:(a) Ku-
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S.; Chen, Q.-A.; Zhou, Y.-G. Chem. Eur. J. 2011, 17, 7193. (j) Chiral
Brønsted acid catalyzed transfer hydrogenation of 3H-indole with
Hantzsch ester as hydrogen source, see: Rueping, M.; Brinkmann, C.;
Antonchick, A. P.; Atodiresel, L. Org. Lett. 2010, 12, 4604. Asymmetric
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(9) (a) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K.Angew.
Chem.,Int. Ed. 2004,43, 1566. (b) Uraguchi, D.; Terada, M.J. Am. Chem.
Soc. 2004,126, 5356. For reviews on chiral phosphoric acid catalysis, see:
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(d) Akiyama, T.Chem. Rev. 2007, 107, 5744. (e) Connon, S. J. An-
gew.Chem., Int. Ed. 2006, 45, 3909. (f) Terada, M. Chem. Commun.
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S.; Freund, M.; Tsogoeva, S. M. Org. Biomol. Chem. 2010,8, 5262.(i)
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ASSOCIATED CONTENT
Supporting Information
Experimental procedures, analytical data for all new compounds,
NMR spectra for the products, HPLC charts, and crystallographic
data for derivatives of 2a, 4a, 4cand 4e (CIF).This material is
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
This work was partially supported by a Grant-in-Aid for Scientific
Research on Innovative Areas “Advanced Transformationby Or-
ganocatalysis” from the Ministry of Education, Culture, Sports,
Science and Technology, Japan, and a Grant-inAid for Scientific
Research from the Japan Society for the Promotion of Science.
We thank Dr. Keiji Mori (Gakushuin Univ.) for X-ray structural
analysis.
(10) Intramolecular hydride transfer reaction of indoline had been re
ported, see: Mao, H.; Xu, R.; Wan, J.; Jiang, Z.; Sun, C.; Pan, Y. Chem.
Eur. J. 2010, 16, 13352.
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