Journal of the American Chemical Society
Article
(7) Yasukawa, T.; Miyamura, H.; Kobayashi, S. J. Am. Chem. Soc.
2012, 134, 16963.
compared with the corresponding homogeneous metal
complexes.28 As notable examples of the superior performance
of the chiral NP systems as heterogeneous chiral catalysts, the
reactions of a wide range of arylboronic acids and α,β-
unsaturated esters, which are known to be difficult to obtain
with high selectivity,13 were conducted with remarkably high
enantioselectivities (>98% ee of 19 examples in 22 examples
tested). Based on the results of ICP analysis and of hot leaching
tests, we ruled out the possibility that leached Rh-diene
complexes function as the active species in the heterogeneous
NP system. Furthermore, various unique phenomena in the
heterogeneous NP system were observed by NLE analysis of
the reaction, by measuring the reaction profiles, and by
determining the effect on the length of the induction periods of
pre-stirring with reductive compounds. These experimental
results demonstrate that there is a clear difference between the
nature of active species in the heterogeneous NP system and
the active species in the homogeneous metal complex system.
Chiral NP systems offer engineering flexibility and have the
potential to be applied to many other reactions promoted by
asymmetric catalysts. We believe the concept of chiral NP
systems as heterogeneous chiral catalysts opens the door to a
new generation of asymmetric catalysts and expect that this
approach will play a central role in this important field.
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ASSOCIATED CONTENT
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S
* Supporting Information
Reaction procedures and spectra. The Supporting Information
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(16) See the Supporting Information for details.
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AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
(20) Crabtree, R. H. Chem. Rev. 2012, 112, 1536.
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ACKNOWLEDGMENTS
■
(22) Negative NLE was observed under the reported conditions
using Rh-BINAP complex in the asymmetric 1,4-addition of
arylboronic acids to enones. It was also reported that Rh-diene
complex could form a dimeric species, but the dimerization constant of
Rh/cyclooctadiene was lower than that of Rh-BINAP complex.
Compared with those reported systems, our conditions utilized
much lower concentration of Rh and higher temperature, which could
shift the equilibrium between monomeric Rh species and dimeric Rh
species to the monomer side, see: (a) Kina, A.; Iwamura, H.; Hayashi,
T. J. Am. Chem. Soc. 2006, 128, 3904. (b) Kina, A.; Yasuhara, Y.;
Nishimura, T.; Iwamura, H.; Hayashi, T. Chem.Asian J. 2006, 1, 707.
(c) Berthon-Gelloz, G.; Hayashi, T. J. Org. Chem. 2006, 71, 8957.
This work was partially supported by a Grant-in-Aid for Science
Research from the Japan Society for the Promotion of Science
(JSPS), Global COE Program, The University of Tokyo,
MEXT, Japan, and the Japan Science and Technology Agency
(JST).
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