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spectrum of {Rh(cod)[(S,S)-L13′]2OTf was also identical to
that of the Rh(I) complex of (S,S)-L13 prepared in situ at a 1:2
molar ratio, indicating the clean formation of a single species in
solution (see SI). Although we are unable to clarify the exact
underlying reason for the outstanding catalytic performance of
this type of Rh catalyst presently, the OH group in the
tautomerized ligand seems to be important in influencing the
electronic and steric scenarios of the Rh(I) center14 by ligand−
ligand or/and ligand−substrate15 interaction(s) through H-
bonding. In fact, the distinct effects of aprotic and protic
solvents on the catalytic outcome using [Rh(cod){(S,S)-
L13′)}2]OTf observed in Table 1 provide circumstantial
evidence for the involvement of H-bonding interactions in
the catalysis.
In conclusion, a class of Rh(I) catalysts containing
monodentate phosphorous acid diesters tautomerized from
the corresponding secondary phosphine oxides has been
discovered by serendipitous acidic hydrolysis of phosphor-
amidite ligands. The evolved catalyst demonstrates excellent
enantioselectivity (98−99% ee) and catalytic activity (catalyst
loading as low as 0.01 mol%) in asymmetric hydrogenations of
a list of α-aryl-/alkyl-substituted ethenylphosphonic acids,
challenging olefinic substrate, providing a facile approach to
the corresponding enantiopure phosphonic acids with signifi-
cant biological interest. The OH groups in two adjacent
monodentate phosphorous acid diester ligands around the Rh
metal center and the related H-bonding interactions might be
beneficial in the catalysis, which will provide a useful basis to
bridge the gap between mono- and bidentate phosphorus
ligands for construction of chiral transition-metal catalysts.15
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ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental procedures, spectral and analytical data for all
products, and crystallographic data (CIF). This material is
Synthesis and Applications; Borner, A., Ed.; Wiley: Weinheim, 2008; pp
̈
831−847. (c) Dubrovina, N. V.; Borner, A. Angew. Chem., Int. Ed.
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2004, 43, 5883.
AUTHOR INFORMATION
■
(11) Examples: (a) Li, G. Y. Angew. Chem., Int. Ed. 2001, 40, 1513.
(b) Bigeault, J.; Giordano, L.; Buono, G. Angew. Chem., Int. Ed. 2005,
44, 4753. (c) Lerebours, R.; Wolf, C. Org. Lett. 2007, 9, 2737.
(d) Nemoto, T.; Fukuyama, T.; Yamamoto, E.; Tamura, S.; Fukuda,
T.; Matsumoto, T.; Akimoto, Y.; Hamada, Y. Org. Lett. 2007, 9, 927.
(e) Reetz, M. T.; Bondarev, O. Angew. Chem., Int. Ed. 2007, 46, 4523.
(f) Landert, H.; Spindler, F.; Wyss, A.; Blaser, H.-U.; Pugin, B.;
Ribourduoille, Y.; Gschwend, B.; Ramalingam, B.; Pfaltz, A. Angew.
Chem., Int. Ed. 2010, 49, 6873.
(12) Girard, C.; Kagan, H. B. Angew. Chem., Int. Ed. 1998, 37, 2922.
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Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the NSFC (Grants 21172237, 21032007, and
21121062) and the Major Basic Research Development
Program of China (Grant 2010CB833300) for support of this
work and Professor Qi-Lin Zhou (Nankai University) for
generously providing enantiopure SiPhos and Spinol.
(14) Gridnev, I. D.; Imamoto, T. Acc. Chem. Res. 2004, 37, 633.
(15) Reviews: (a) Breit, B. Angew. Chem., Int. Ed. 2005, 44, 6816.
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