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For further asymmetric syntheses of amines with a stereogenic center in α-position to N see: a) J. A. Ellman, T. D. Owens, T. P. Tang, Acc. Chem. Res. 2002, 35, 984;
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P. A. Evans et al. have prepared corresponding N-tosyl derivatives by stereoconservative Rh-catalyzed allylic substitution at enantioenriched derivatives of allylic alcohols, which does not constitute an asymmetric synthesis. Surveys: a) D. K. Leahy, P. A. Evans in Modern Rhodium-Catalyzed Organic Reactions (Ed.: P. A. Evans), Wiley, New York, 2005, p. 191;
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Leahy, D.K.1
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4043070494
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The absolute configurations of the products described herein were as anticipated (Ref. [8]); for independent determinations see a) M. Atobe, N. Yamazaki, C. Kibayashi, J. Org. Chem. 2004, 69, 5595;
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33
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33748675398
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note
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For substrate 1a (in combination with L2) a reaction time of 2.5 h was required to give the substitution product in 87 % yield with 98% ee and a regioselectivity of 96:4.
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34
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0000631448
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a) R. D. Connell, T. Rein, B. Åkermark, P. Helquist, J. Org. Chem. 1988, 53, 3845;
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Gagné, M.R.5
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36
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0035804985
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2, which has previously been used in Pd-catalyzed allylic substitutions (Y. Wang, K. Ding, J. Org. Chem. 2001, 66, 3238).
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Wang, Y.1
Ding, K.2
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37
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84989431741
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To our knowledge, this compound has not been previously described. We prepared it according to a general procedure (Y. Lin, S. A. Lang, Jr, Synthesis 1980, 119) in 88% yield.
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(1980)
Synthesis
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Lin, Y.1
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38
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41
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33748673473
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note
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The ee values of the free amines were determined and found to agree, within the range of precision, with those of the protected precursors.
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42
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1442360753
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(Ed.: R. H. Grubbs), Wiley, New York
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