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Racemization of immes derived from amino esters is a problem often encountered when these compounds are used as sub-strates for the Staudinger reaction. For a recent example, see: C. Niu, T. Petterson, M. J. Miller, J Org. Chem. 1996, 61, 1014-1022. In fact, when the imine was prepared in boiling benzene, total racemization was observed. Conditions used throughout this work ensured that the imine was obtained and used without racemization.
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The low selectivity obtained when the controlling chiral center is that at the imine nitrogen moiety is a general feature of the Staudinger reaction. The exception are those imines with bulky substituents attached to the chiral group at the nitrogen atom. For an exhaustive discussion, see: G. I. Georg, V T Ravikumarin in The Organic Chemistry of β-Lactams (Ed.: G. I. Georg), VCH Publishers, Inc. New York, 1992, chapter 4.
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85088279506
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1H-NMR using tris[3-(heptafluoropropylhy-droxymethylene)-(+)-camphorato]europium(III). The enantiomer ratio of the final product was found to be identical to the diastereomer ratio of the starting material 5.
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42
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85088280774
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The intermolecular Heck coupling of aryl halides and dehydroalanine derivatives is well-established. See: [29a] J. H. Dygos, E. E. Yonan, M. G. Scaros, O. J. Goodmonson, D. P. Getman, R. A. Periana, G. R. Beck, Synthesis 1992, 741-743. - [29b] M. Cutolo, V. Fiandanese, F. Naso, O. Sciacovelli, Tetrahedron Lett. 1983, 24, 4603-4606. - [29c] A.-S. Carlström, T. Frejd, Synthesis 1989, 414-418. - A very recent intramolecular example: [29d] S. E. Gibson (née Thomas), N. Guillo, R. J. Middleton, A. Thuilliez, M. J. Tozer, J. Chem. Soc., Perkin Trans. I 1997, 447-455.
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The intermolecular Heck coupling of aryl halides and dehydroalanine derivatives is well-established. See: [29a] J. H. Dygos, E. E. Yonan, M. G. Scaros, O. J. Goodmonson, D. P. Getman, R. A. Periana, G. R. Beck, Synthesis 1992, 741-743. - [29b] M. Cutolo, V. Fiandanese, F. Naso, O. Sciacovelli, Tetrahedron Lett. 1983, 24, 4603-4606. - [29c] A.-S. Carlström, T. Frejd, Synthesis 1989, 414-418. - A very recent intramolecular example: [29d] S. E. Gibson (née Thomas), N. Guillo, R. J. Middleton, A. Thuilliez, M. J. Tozer, J. Chem. Soc., Perkin Trans. I 1997, 447-455.
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The intermolecular Heck coupling of aryl halides and dehydroalanine derivatives is well-established. See: [29a] J. H. Dygos, E. E. Yonan, M. G. Scaros, O. J. Goodmonson, D. P. Getman, R. A. Periana, G. R. Beck, Synthesis 1992, 741-743. - [29b] M. Cutolo, V. Fiandanese, F. Naso, O. Sciacovelli, Tetrahedron Lett. 1983, 24, 4603-4606. - [29c] A.-S. Carlström, T. Frejd, Synthesis 1989, 414-418. - A very recent intramolecular example: [29d] S. E. Gibson (née Thomas), N. Guillo, R. J. Middleton, A. Thuilliez, M. J. Tozer, J. Chem. Soc., Perkin Trans. I 1997, 447-455.
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The intermolecular Heck coupling of aryl halides and dehydroalanine derivatives is well-established. See: [29a] J. H. Dygos, E. E. Yonan, M. G. Scaros, O. J. Goodmonson, D. P. Getman, R. A. Periana, G. R. Beck, Synthesis 1992, 741-743. - [29b] M. Cutolo, V. Fiandanese, F. Naso, O. Sciacovelli, Tetrahedron Lett. 1983, 24, 4603-4606. - [29c] A.-S. Carlström, T. Frejd, Synthesis 1989, 414-418. - A very recent intramolecular example: [29d] S. E. Gibson (née Thomas), N. Guillo, R. J. Middleton, A. Thuilliez, M. J. Tozer, J. Chem. Soc., Perkin Trans. I 1997, 447-455.
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