Structure and Reactivity of Lithiated α-Amino Nitriles
1998; Wiley; Volume: 1998; Issue: 1 Linguagem: Inglês
10.1002/(sici)1099-0690(199801)1998
ISSN1434-193X
AutoresDieter Enders, Jochen Kirchhoff, Peter Gerdes, Dietrich Mannes, Gerhard Raabe, Jan Runsink, Gernot Boche, Michael Marsch, H. AHLBRECHT, Horst Sommer,
Tópico(s)Chemical Reaction Mechanisms
ResumoEuropean Journal of Organic ChemistryVolume 1998, Issue 1 p. 63-72 Full Paper Structure and Reactivity of Lithiated α-Amino Nitriles Dieter Enders, Dieter Enders Enders@RWTH-Aachen.de Search for more papers by this authorJochen Kirchhoff, Jochen Kirchhoff Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorPeter Gerdes, Peter Gerdes Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorDietrich Mannes, Dietrich Mannes Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorGerhard Raabe, Gerhard Raabe Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorJan Runsink, Jan Runsink Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorGernot Boche, Gernot Boche Boche@ps1515.chemie.uni-marburg.de Fachbereich Chemie, Philipps Universität, Hans-Meerwein-Str., D-35032 Marburg, Fax: (internat.) + 49(0)6421/288917Search for more papers by this authorMichael Marsch, Michael Marsch Fachbereich Chemie, Philipps Universität, Hans-Meerwein-Str., D-35032 Marburg, Fax: (internat.) + 49(0)6421/288917Search for more papers by this authorHubertus Ahlbrecht, Hubertus Ahlbrecht Hubertus.Ahlbrecht@org.chemie.uni-giessen.de Institut für Organische Chemie, Justus Liebig Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Fax: (internat.) + 49(0)641/9934309Search for more papers by this authorHorst Sommer, Horst Sommer Institut für Organische Chemie, Justus Liebig Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Fax: (internat.) + 49(0)641/9934309Search for more papers by this author Dieter Enders, Dieter Enders Enders@RWTH-Aachen.de Search for more papers by this authorJochen Kirchhoff, Jochen Kirchhoff Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorPeter Gerdes, Peter Gerdes Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorDietrich Mannes, Dietrich Mannes Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorGerhard Raabe, Gerhard Raabe Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorJan Runsink, Jan Runsink Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Straße 1, D-52074 Aachen, Fax: (internat.) + 49(0)241/8888127Search for more papers by this authorGernot Boche, Gernot Boche Boche@ps1515.chemie.uni-marburg.de Fachbereich Chemie, Philipps Universität, Hans-Meerwein-Str., D-35032 Marburg, Fax: (internat.) + 49(0)6421/288917Search for more papers by this authorMichael Marsch, Michael Marsch Fachbereich Chemie, Philipps Universität, Hans-Meerwein-Str., D-35032 Marburg, Fax: (internat.) + 49(0)6421/288917Search for more papers by this authorHubertus Ahlbrecht, Hubertus Ahlbrecht Hubertus.Ahlbrecht@org.chemie.uni-giessen.de Institut für Organische Chemie, Justus Liebig Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Fax: (internat.) + 49(0)641/9934309Search for more papers by this authorHorst Sommer, Horst Sommer Institut für Organische Chemie, Justus Liebig Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Fax: (internat.) + 49(0)641/9934309Search for more papers by this author First published: January 1998 https://doi.org/10.1002/(SICI)1099-0690(199801)1998:1 3.0.CO;2-HCitations: 54AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract Investigations aimed at elucidating the structure of lithiated α-amino nitriles B have led to the identification of N-lithio α-amino nitrile anions as characteristic structural features. Their preparations, crystal structures, and solution structures under the reaction conditions, are described. X-ray crystal structure analyses of crystalline 3 and (S, S)-4 reveal the presence of dimeric aggregates B4 with Ci symmetry, held together by four-membered NLiNLi rings, coordinatively saturated at lithium by four THF ligands. The crystal structure of (S, S)-6 shows polymeric aggregation with dimeric subunits similar to those of 3 and (S, S)-4. The solution structure has been investigated by IR and Raman spectroscopy of 2, (S, S)-4 and (S, S)-6, by NMR spectroscopy of 3, (S, S)-5 and (S, S)-6, and by cryoscopic measurements of (S, S)-6 in THF. Trapping experiments complement the results. In THF, which constitutes the principal reaction medium, the lithiated amino nitriles B are found to exist as monomeric species B6 between −110 and +25°C. In less polar solvents, higher aggregation is presumed. NMR spectroscopic studies of 3 show that the favored orientations of the amine and phenyl groups are similar to their conformations in the solid state. In the light of the results obtained, a transition state is proposed to account for the relative topicity observed in the 1,4-additions of enantiopure lithiated α-amino nitriles (S, S)-4, (S, S)-5, and (S, S)-6 to Michael acceptors. Citing Literature Volume1998, Issue1January 1998Pages 63-72 RelatedInformation
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