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(ethyl acetate/hexane), yielding the desired secondary alcohol,
which crystallized upon standing at low temperature (fridge). The
residue was analyzed by chiral HPLC.
4.11. General procedure for the kinetic studies of the
racemization reaction
3. (a) Góis, P. M.P.;Trindade,A. F.;Veiros,L.F.;André, V.;Duarte,M.T.;Afonso, C.A. M.;
Caddick, S.; Cloke, F. G. N. Angew. Chem., Int. Ed. 2007, 46, 5750; (b) Trindade, A. F.;
Góis, P. M.P.;Veiros, L.F.;André,V.;Duarte,M.T.;Afonso, C.A. M.;Caddick, S.; Cloke,
F. G. N. J. Org. Chem. 2008, 73, 4076.
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5. Farrugia, L. J. Appl. Crystallogr. 1997, 30, 565.
6. (a) Wiberg, K. B. Tetrahedron 1968, 24, 1083.Wiberg indices are electronic pa-
rameters related to the electron density between atoms. They can be obtained
from a Natural Population Analysis and provide an indication of the bond
strength.
To a solution of complex 6 (1 mol %) in tert-amyl alcohol (2.5 ml),
was added KOtBu (10 mol %) and 1-phenyl ethanol (1 equiv). The
mixture was allowed to react at 80 ꢀC and samples were collected at
the given times and analyzed by chiral HPLC. Chiralcel OD column,
eluent: 10% isopropanol in hexane, acetophenone Rf¼6.6 min, (R)-1-
phenyl ethanol Rf¼10.2 min and (S)-1-phenyl ethanol Rf¼12.9 min.
7. (a) Carpenter, J. E.; Weinhold, F. J. Mol. Struct. (Theochem) 1988, 169, 41; (b)
Carpenter, J.E. PhD Thesis, University of Wisconsin Madison WI, 1987; (c) Foster,
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(g) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899; (h) Wein-
hold, F.; Carpenter, J. E. The Structure of Small Molecules and Ions; Plenum: New
York, NY, 1988; p 227.
4.12. Computational details
Calculations were performed using the Gaussian 98 software
package13 and the B3PW91 hybrid functional, without symmetry
constraints. That functional includes a mixture of HartreeeFock14
exchange with DFT exchange-correlation,15 given by Becke’s three
parameter functional16 with Perdew and Wang’s 1991 gradient-
corrected correlation functional.17 The LanL2DZ basis set18 aug-
mented with an f-polarization function19 was used for Rh, and
a standard 6-31G(d,p)20 for the remaining elements. A Natural
Population Analysis (NPA)7 and the resulting Wiberg indices6 were
used for a detailed study of the electronic structure and bonding of
the optimized species. Atomic coordinates for all optimized struc-
ture are in the Supplementary data.
8. Lloret, J.; Carbó, J. J.; Bo, C.; Lledós, A.; Pérez-Prieto, J. Organometallics 2008, 27,
2873.
9. For examples of enantioselective rhodium catalyzed aldehydes arylations
reactions see: (a) Duan, H. F.; Xie, J. H.; Shi, W. J.; Zhang, Q.; Zhou, Q. L. Org. Lett.
2006, 8, 1479; (b) Jagt, R. B. C.; Toullec, P. Y.; de Vries, J. G.; Feringa, B. L.;
Minnaard, A. J. Org. Biomol. Chem. 2006, 4, 773; (c) Martina, S. L. X.; Jagt, R. B. C.;
de Vries, J. G.; Feringa, B. L.; Minnaard, A. J. Chem. Commun. 2006, 4093; (d)
Nishimura, T.; Kumamoto, H.; Nagaosa, M.; Hayashi, T. Chem. Commun. 2009,
5713; (e) Noel, T.; Vandyck, K.; Van der Eycken, J. Tetrahedron 2007, 63, 12961.
10. (a) Davies, H. M. L.; Beckwith, R. E. J. Chem. Rev. 2003, 103, 2861; (b) Góis, P. M. P.;
Afonso, C. A. M. Eur. J. Org. Chem. 2004, 3773.
11. Dinh, P. M.; Howarth, J. A.; Hudnott, A. R.; Williams, J. M. J.; Harris, W. Tetra-
hedron Lett. 1996, 37, 7623.
12. Arduengo, A. J., III; Krafczyk, R.; Schmutzer, R.; Craig, H. A.; Goerlich, J. R.;
Marshall, W. J.; Unverzagt, M. Tetrahedron 1999, 55, 14523.
4.13. Crystallographic data
13. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.;
Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.;
Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.;
Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.;
Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.;
Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.;
Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.;
Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle,
E. S.; Pople, J. A. Gaussian 98, Revision A.7; Gaussian,: Pittsburgh, PA, 1998; and
provide an indication of the bond strength.
Crystallographic data (excluding structure factors) for the
structure(s) reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publi-
cation no. CCDC 741791 and CCDC 741792. Copies of the data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK [fax.: (internet.) þ44 1223/336 033; e-mail:
Acknowledgements
14. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital
Theory; John Wiley & Sons: New York, NY, 1986.
15. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford
University: New York, NY, 1989.
We thank to FCT (POCI 2010) and FEDER (SFRH/BD/30619/2006,
PTDC/QUI/66695/2006, and PTDC/QUI/66015/2006) for financial
support.
16. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
17. (a) Burke, K.; Perdew, J. P.; Wang, Y. In Electronic Density Functional Theory:
Recent Progress and New Directions; Dobson, J. F., Vignale, G., Das, M. P., Eds.;
Plenum: New York, NY, 1998; (b) Perdew, J. P. In Electronic Structure of Solids ’91;
Ziesche, P., Eschrig, H., Eds.; Akademie: Berlin, 1991; p 11; (c) Perdew, J. P.;
Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais,
C. Phys. Rev. B 1992, 46, 6671; (d) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.;
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4978; (e) Perdew, J. P.; Burke, K.; Wang, Y. Phys. Rev. B 1996, 54, 16533.
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Supplementary data
Supplementary data associated with this article can be found in
MOL files and InChIKeys of the most important compounds de-
scribed in this article.
References and notes
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