Asymmetric thermal transformation, a new way to enantiopure biphenyl- bridged titanocene and zirconocene complexes: Efficient catalysts for asymmetric imine hydrogenation

Journal of the American Chemical Society

Volumn 121, Issue 7, 1999, Pages 1524-1527

  Ringwald, Markus ^a,b   Stürmer, Rainer ^c   Brintzinger, Hans H ^a  

^a UNIVERSITY OF KONSTANZ   (Germany)

^b MCAT GmbH   (Germany)

^c BASF SE   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

IMINE; METAL COMPLEX; TITANIUM DERIVATIVE; ZIRCONIUM DERIVATIVE;

ARTICLE; CATALYSIS; ENANTIOMER; HYDROGENATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0039772398     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983524w     Document Type: Article

References (40)

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22. The assignment of these diastereomers follows that of the corresponding Ti complexes reported in ref 9.
23. 1H NMR experiments were conducted with toluene or hexamethylbenzene as internal NMR standard, to ensure that the disappearance of one diastereomer is accompanied by an increase of the other one and not just by destruction of the complex.
24. 9
25. 2 under liberation of the biphenylbridged ligand. Reaction with Moshers reagent failed similarly.
26. 2 (see Experimental Section).
27. 4
28. 4
29. 2, which is then reacted with (R)-(+)-1-phenyl-1-propanol as described above.
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33. While indefinitely stable as crystals in a nitrogen or argon atmosphere, the zirconocene complexes gradually decompose in the presence of air.
34. 2 was likewise found to be configurationally stable in toluene solution at 50 °C even in the presence of excess methylalumoxane.
35. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1992, 114, 7562; Willoughby, C. A.; Buchwald, S. L. J. Org. Chem. 1993, 58, 7627. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8952. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 11703. Recently, increased yields and enantioselectivities have been reported for imine hydrosilylations at catalyst:substrate ratios similar to those used here: Verdaguer, X.; Lange, U. E. W.; Reding, M. T.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 6784. Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. Engl. 1998, 37, 1103.
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39. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1992, 114, 7562; Willoughby, C. A.; Buchwald, S. L. J. Org. Chem. 1993, 58, 7627. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8952. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 11703. Recently, increased yields and enantioselectivities have been reported for imine hydrosilylations at catalyst:substrate ratios similar to those used here: Verdaguer, X.; Lange, U. E. W.; Reding, M. T.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 6784. Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. Engl. 1998, 37, 1103.
40. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1992, 114, 7562; Willoughby, C. A.; Buchwald, S. L. J. Org. Chem. 1993, 58, 7627. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8952. Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 11703. Recently, increased yields and enantioselectivities have been reported for imine hydrosilylations at catalyst:substrate ratios similar to those used here: Verdaguer, X.; Lange, U. E. W.; Reding, M. T.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 6784. Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. Engl. 1998, 37, 1103.