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Scheme 1. Synthesis of chiral ferrocenyl secondary amines and phosphoramidite ligands.
Table 1. Asymmetric hydrosilylation of styrenes using L3.a
Government (2011-0010550) and by Basic Science
Research Program (2012R1A6A1029029).
Supporting Information. Experimental details and analyt-
ical data are available in the online version of this article.
References
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Entry
Ligands
Substrate
R
Yieldb (%)
% eec
1
2
3
4
5
6
7d
8
a
L3a
L3b
L3c
L3d
L3a
L3a
L3a
L3a
5a
5a
5a
5a
5b
5c
5d
5e
H
H
H
H
4-CH3
2-CH3
4-MeO
4-Cl
85
41
85
93
97
96
99
91
91 (R)
62 (R)
73 (R)
68 (S)
72 (R)
97 (R)
91 (R)
91 (R)
Hydrosilylation was performed with 2.0 mmol of 5 at 20 ꢀC in
20 h. The catalyst was generated in situ by mixing [PdCl(π-C3H5)]2
and L3. The initial ratio of 5/HSiCl3/Pd/L3 was 1.0/1.2/0.010/0.020.
Isolated yield of 6 by bulb-to-bulb distillation.
b
c
Determined by HPLC analyses of 7 with a chiral stationary column
(Daicel Chiralpak OD-H, OB-H and AD-H).
d
Reaction was completed within 1 h.
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Soc. Rev. 2008, 37, 839; (d) J. F. Teichert, B. L. Feringa,
Angew. Chem. Int. Ed. 2010, 49, 2486.
obtained in the reaction of 2-methylstyrene (5c) (entry 6).
We found that the reactivities and enantioselectivities were
good enough for 4-methoxystyrene and 4-chlorostyrene
6. (a) J. F. Jensen, B. Y. Svendsen, T. V. la Cour,
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(entries
7 and 8). Notably, the hydrosilylation of
4-methoxystyrene showed a high catalytic activity. The
reaction was completed within 1 h at 20ꢀC.
In summary, it is demonstrated that
a palladium
catalyst coordinating with phosphoramidite ligand (Sa,Rc,Rc,)-
L3a from (S)-BINOL and chiral bis((R)-1-ferrocenylethyl)
amine shows a high catalytic activity and enantioselectivity
up to 97% ee in asymmetric hydrosilylation of styrene and its
derivatives. The hydrosilylation of various olefin substrates
using these ligands is in progress.
Acknowledgments. This work was supported by National
Research Foundation of Korea Grant funded by the Korean
9. H.-S. Park, S. Namgung, H. M. Shin, H. J. Ahn, J. W. Han,
Bull. Korean Chem. Soc. 2014, 35, 2243.
Bull. Korean Chem. Soc. 2016, Vol. 37, 795–796
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