Carbanionic chemistry and enantioselective synthesis

Carbanionic chemistry and enantioselective synthesis: Development of new methods in enantioselective synthesis; chiral 1-oxy-allyl, -benzyl, and -alkyl anions: homoaldol reaction; chiral recognition by bases; synthesis of dipeptide isosteres and other potentially biologically active compounds, N-Sulfonyl-1,3-oxazolidines as chiral templates, transformation of these reactions to solid phase.

Drittmittelgeber:

Fonds der Chemischen Industrie, Bayer AG, Deutsche Forschungsgemeinschaft, Graduiertenkolleg "Hochreaktive Mehrfachbindungssysteme", Sonderforschungsbereich 424 "Molekulare Orientierung als Funktionskriterium in chemischen Systemen", Alexander von Humboldt - Stiftung.

Veröffentlichungen:

M. Oestreich, D. Hoppe: "(-)-Sparteine-Mediated Stereoselective Intramolecular Conjugate Addition Reactions of Dienes and Enynes", Tetrahedron Lett. 1999, 40, 1881-1884

A. Deiters, D. Hoppe: "Chiral Induction by Elimination-Coupled Lithium-Ene Reaction: Synthesis of (+)-(3R,4R)-1,2-Dihydromultifidene", Angew. Chem. 1999, 111, 529-532; Angew. Chem. Int. Ed. Engl. 1999, 38, 546-548.

J. van Bebber, H. Ahrens, R. Fröhlich, D. Hoppe: "Efficient Desymmetrization of meso-cis-1,2-Cyclohexanedimethanol with Differentiation between Diastereotopic and Enantiotopie C-H Bonds by (-)-Sparteine-Mediated Deprotonation", Chem. Eur. J. 1999, 5, 1905-1916.

J. Schwerdtfeger, S. Kolczewski, B. Weber, R. Fröhlich, D. Hoppe: "Stereoselective Deprotonation of Chiral and Achiral 2-Aminoalkyl Carbamates. Synthesis of Optically Active b-Aminoalkanols via 1-Oxy-Substituted Alkyllithium Intermediates", Synthesis 1999, 1573-1592

B. Weber, S. Kolczewski, R. Fröhlich, D. Hoppe: "Facile and Highly Stereoselective Synthesis of the C₂-Symmetrical Diamino Diol Core-Unit of HIV-1 Protease Inhibitors and of Their Symmetrical and Unsymmetrical Analogues from Lithiated 2-(Dibenzylamino)alkyl Carbamates Oxidative Dimerization", Synthesis 1999, 1593-1606.

E.-U. Würthwein, K. Behrens, D. Hoppe: "Enantioselective Deprotonation of Alkyl Carbamates by Means of (R,R)-1,2-Bis(N,N-dimethylamino)cyclohexane/sec-Butyllithium - Theory and Experiment." Chem. Eur. J. 1999, 5, 3459-3463.

T. Heinl, S. Retzow, D. Hoppe, G. Fraenkel, A. Chow: "Experimental and Theoretical Investigations of Lithio-Indenyl Carbamate/(-)-Sparteine and (-)-a-Isosparteine Complexes", Chem. Eur. J. 1999, 5, 3464-3470.

B. Weber, J. Schwerdtfeger, R. Fröhlich, A. Göhrt, D. Hoppe: "Diastereoselective Lithiation and Substitution of (S)-N-Benzylprolinol and rac-N-Benzylpiperidine-2-methanol via the Carbamate Esters. Kinetic Resolution by means of (-)-Sparteine-mediated Deprotonation." Synthesis 1999, 1915-1924.

C. Derwing, H. Frank, D. Hoppe: "Chiral Benzyllithium Compounds: High Configurative Stability of (R)- and (S)-1-Lithioindan-1-yl N,N-Diisopropylcarbamate and Unexpected Stereochemical Course of the Substitution Reactions", Eur. J. Org. Chem. 1999, 3519-3524.

D. Hoppe, M.J. Woltering, M. Oestreich, R. Fröhlich: "(-)-Sparteine-mediated Asymmetric Intramolecular Carbolithiation of Alkenes - Synthesis of Enantiopure Cyclopentanes with Three Consecutive Stereogenic Centers", Helv. Chim. Acta 1999, 82, 1860-1877.

M. Oestreich, R. Fröhlich, D. Hoppe: "(-)-Sparteine-mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes", J. Org. Chem. 1999, 64, 8616-8626.

S.H. Kleinfeld, E. Wegelius, D. Hoppe: "(- )-Sparteine-mediated Asymmetric Cyclocarbolithiation of Alkenes Combined with a Stereospecific Retro-[1,4]-Brook-Rearrangement", Helv. Chim. Acta, 1999, 82, 2413-2424.

F. Marr, R. Fröhlich, D. Hoppe: "A Highly Enantioenriched, Configurationally Stable a-Thioallyllithium Compound and the Stereochemical Course of Its Electrophilic Alkylation", Org. Lett. 1999, 1, 2081-2084.

O. Stratmann, D. Hoppe, R. Fröhlich: "Synthesis and Structure of Highly Enantio- and Diastereoenriched 1-Aza-4-oxa-7-thiabcyclo[3.3.0]octan-8-ones Derived from Acyl-Substituted S-Benzyl Thiocarbamates", J. Prakt. Chem. 2000, 342, 828-831.

A. Kreier, R. Fröhlich, E. Wegelius, D. Hoppe: "Asymmetric Synthesis of Stereodefined 7-(Alk-1-enyl)-5,6,7,8-tetrahydronaphthalene-2-carboxylic Acids and Their Precursors, Bearing a Polar Group in 8-Position, by the 3-Sulfonyl-1,3-oxazolidine Method", Synthesis 2000, 1391-1402.

A. Deiters, R. Fröhlich, D. Hoppe: "Enantioselective Synthesis of Functionalized 1,5-Cyclononadienes by Intramolecular Cycloalkylation by Means of a,a-Diallylcoupling", Angew. Chem. 2000, 112, 2189-2192; Angew. Chem. Int. Ed. Engl. 2000, 39, 2105-2107.

A. Deiters, C. Mück-Lichtenfeld, R. Fröhlich, D. Hoppe: "Asymmetric Synthesis of a (2Z,7E)-Cyclononadiene by an Intramolecular Cycloalkylation and Insights to Its Conformational Properties", Org. Lett. 2000, 2, 2415-2418.

D. Heimbach, R. Fröhlich, B. Wibbeling, D. Hoppe: "Asymmetric Lithiation of an Allyl Carbamate by an Complexing Remote Chiral Substituent", Synlett 2000, 950-954.

K.R.K. Prasad, D. Hoppe: "Applications of Homoallylic Alcohols Derived from (-)-Sparteine-Mediated Asymmetric Homoaldolization: Entry to 5- to 8-Membered Oxacycles through Metathesis Reaction", Synlett 2000, 1067-1069.

F. Steif, B. Wibbeling, O. Meyer, D. Hoppe: "Enantio- and Diastereoselective Synthesis of (Protected) 2-Formyl- and 2-(Hydroxymethyl)-1-phenyl-1,3-alkanediols from Chiral 2-Methoxy-3-tosyl-1,3-oxazolidines by Subsequent Asymmetric Formylation and Aldolization", Synthesis 2000, 743-753.

C. Redecker, U. Altrup, D. Hoppe, R. Düsing, E.-J. Speckmann: "Effects of Valproate Derivatives: I. Antiepileptic Efficacy of Amides, Structural Analogs and Esters", Neuropharmacology 2000, 39, 254-266.

C. Redecker, U. Altrup, D. Hoppe, T. Hense, A. Kreier, A. Rabe, R. Düsing, E.-J. Speckmann: "Effects of Valproate Derivatives: II. Antiepileptic Efficacy in Relation to Chemical Structures of Valproate Sugar Esters", Neuropharmacology 2000, 39, 267-281.

Dissertations:

M. Oestreich: "(-)-Spartein-vermittelte stereoselektive intramolekulare Carbolithiierung von in Allyl- oder Propargyl-Stellung funktionalisierten Mehrfachbindungssystemen"

J. van Bebber: "Desymmetrisierung und stereoselektive C-Substitution von meso-1,4-Diolen durch (- )-Spartein-induzierte Deprotonierung ihrer Dicarbamate"

S. Kleinfeld: "Stereoselektive Substitution an chiralen a -Lithio-alkylcarbamaten durch Retro-[1,4]-Brook-Umlagerung"

E. Galler: "Enantioselektive Synthese von Benzylalkoholen mit chiralen dilithiierten N-Monoalkylcarbamidsäurebenzylestern"

F. Steif: "Diastereoselektive Aldolreaktionen für die Synthese von enantiomerenreinen Triolen mit N-Tosyl-1,3-oxazolidinen"

O. Stratmann: "Stereochemische Untersuchungen an einem enantiomerenreinen und konfigurativ stabilen a-Thiobenzyllithium-Derivat"

A. Kreier: "Auxiliargesteuerte asymmetrische Synthese von potentiellen Microcystin-Mimetika mit N-Sulfonyl-1,3-oxazolidinen"

J.G. Peters: "Untersuchungen zur enantioselektiven Carbolithiierung von 1-arylsubstituierten 1-Alkenyl-N,N-dialkylcarbamaten"

A. Deiters: "Enantioselektive intramolekulare Allyllithium-Allylchlorid-Kupplungen - Synthese von drei- bis neungliedrigen Carbocyclen"

H. Laqua: "Untersuchungen zur asymmetrischen intramolekularen Carbolithiierung von g-Indenylalkylcarbamaten"

D. Heimbach: "Lithiierte, Oxazolidin-substituierte 2-Alkenylcarbamate - Synthese, Reaktionsweise und Anwendung in der asymmetrischen Homoaldol-Reaktion"