Fachbereich 12 - Chemie und Pharmazie
Organisch-Chemisches Institut
Professor Dr. Dieter Hoppe

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, enantioselective protonation reactions, transformation of these reactions to solid phase.

Drittmittelgeber:

Fonds der Chemischen Industrie, Bayer AG, Deutsche Forschungsgemeinschaft, Sonderforschungsbereich 424 "Molekulare Orientierung als Funktionskriterium in chemischen Systemen", Internationales Graduiertenkolleg "Template Directed Chemical Synthesis", NRW Graduate School of Chemistry, Alexander von Humboldt-Stiftung.

Veröffentlichungen:

M. Kauch, D. Hoppe, “Synthesis of Substituted Phenols by Directed ortho-Lithiation of in situ N-Silyl-Protected O-Aryl-N-monoalkylcarbamates“, Can. J. Chem. 2001, 79, 1736-1746.

C. Schultz-Fademrecht, B. Wibbeling, R. Fröhlich, D. Hoppe, “Synthesis of Enantiomerically Enriched Allenes by (–)-Sparteine-Mediated Lithiation of Alkynyl Carbamates“, Org. Lett. 2001, 3, 1221-1224.

H. Laqua, R. Fröhlich, B. Wibbeling, D. Hoppe, “Synthesis of Enantioenriched Indene-Derived Bicyclic Alcohols and Tricyclic Cyclopropanes via (–)-Sparteine-Mediated Lithiation of a Racemic Precursor and Kinetic Resolution During the Cyclocarbolithiation“, J. Organomet. Chem. 2001, 624, 96-104.

M. Oestreich, D. Hoppe, “Stereospecific Preparation of Highly Enantiomerically Enriched Organomagnesium Reagents“, Chemtracts - Organic Chemistry 2001, 14, 100-105.

A. Deiters, D. Hoppe, “Asymmetric Synthesis of cis-1,2-Dialkenyl-Substituted Cyclopentanes via (–)-Sparteine-Mediated Lithiation and Cycloalkylation of a 9-Chloro-2,7-nonadienyl Carbamate“, J. Org. Chem. 2001, 66, 2842-2849.

A. Deiters, B. Wibbeling, D. Hoppe, “Enantio- and Diastereoselective Synthesis of a 3,4-Divinylpyrrolidine via Asymmetric Deprotonation and Cyclization of a 9-Chloro-5-aza-2,7-nonadiene“, Adv. Synth. Catal. 2001, 181-183.

M. Brüggemann, C. Holst, D. Hoppe, “First Enantioselective Total Synthesis of Both (+)- and (–)-Metachromin A“, Eur. J. Org. Chem. 2001, 647-654.

O. Stratmann, B. Kaiser, R. Fröhlich, O. Meyer, D. Hoppe, “Configurational Stability of an Enantioenriched a-Thiobenzyllithium Derivative and Stereochemical Course of Its Electrophilic Substitution Reactions. Synthesis of Enantiomerically Pure Tertiary Benzylic Thiols“, Chem. Eur. J. 2001, 423-435.

J. G. Peters, M. Seppi, R. Fröhlich, B. Wibbeling, D. Hoppe, “Stereoselective Intermolecular Carbolithiation of Open-Chain and Cyclic 1-Aryl-1-alkenyl N,N-Diisopropylcarbamates Coupled with Electrocyclic Substitution. Observation of p-Carboxylation in a Benzyllithium Derivative“, Synthesis 2002, 381-392.

M. Özlügedik, J. Kristensen, B. Wibbeling, R. Fröhlich, D. Hoppe, “Nonracemic, Chiral Homoenolate Reagents Derived from (Cycloalk-1-enyl)methyl Carbamates and Evaluation of Their Configurational Stabilities“, Eur. J. Org. Chem. 2002, 414-427.

M. Brüggemann, R. Fröhlich, B. Wibbeling, C. Holst, D. Hoppe, “Stereoselective Formation of Quarternary Carbon Centres with Chiral 3-Sulfonyl-1,3-oxazolidines and Titanium Enolates“, Tetrahedron 2002, 58, 321-340.

C. Schultz-Fademrecht, M. A. Tius, S. Grimme, B. Wibbeling, D. Hoppe, “Synthese enantiomerenangereicherter hochsubstituierter 5-Alkyliden-2-cyclopentenone aus chiralen Allenylcarbamaten. Gleichzeitige Erzeugung chiraler Lithiumallenolate und Aktivierung einer Allylposition für die konrotatorische 4p-Elektrocyclisierung“, Angew. Chem. 2002, 41, 1532-1535.

A. Deiters, C. Mück-Lichtenfeld, R. Fröhlich, D. Hoppe, “Planar-Chiral (2E,7Z)- and (2Z,7E)-Cyclonona-2,7-dien-1-yl Carbamates by Asymmetric Bis-Allylic a,a'-Cycloalkylation - Studies on Their Conformational Stability“, Chem. Eur. J. 2002, 8,1833-1842.

G. Christoph, D. Hoppe, “Asymmetric Synthesis of 2-Alkenyl-1-cyclopentanols via Tin-Lithium Exchange and Intramolecular Cycloaddition“, Org. Lett. 2002, 4, 2189-2192.

G. Gralla, B. Wibbeling, D. Hoppe, “Synthesis of an Ethynyl Carbamate and Application for the Enantioselective Cyclocarbolithiation“, Org. Lett. 2002, 4, 2193-2195.

F. Marr, R. Fröhlich, B. Wibbeling, Ch. Diedrich, D. Hoppe “The Synthesis and Configurational Stability of Enantioenriched a-Thioallyllithium Compounds and the Stereochemical Course of Their Electrophilic Substitutions“, Eur. J. Org. Chem. 2002, 2970-2988.

F. Marr, R. Fröhlich, D. Hoppe “Preparation of Meso-1,3-diphenylallyllithiumú(–)- sparteine Its crystal structure and reactions Tetrahedron: Asymmetry 2002, 13, 2587-2592.

Marr, D. Hoppe “Synthesis of Enantiomerically Enriched Tertiary 2-Cyclohexene-1-thiols via Configurationally Stable a-Thio-Substituted Allyllithium Compounds“ Organic Letters 2002, 24, 4217-4220.

G. Christoph, D. Hoppe “Asymmetric Deprotonation with Alkyllithium/(–)-Sparteine“, Review in The Chemistry of Functional Groups (Hrsg. S. Patai, Z. Rappoport), 2003, Interscience Publishers, Wiley & Sons, in press.

F. Marr, M. Brüggemann, D. Hoppe “a-Oxy-Substituted Lithium Carbanions“, Review in Topics in Organometallic Chemistry (Hrsg. D. M. Hodgson), 2003, Springer-Verlag, im Druck.

DISSERTATIONS:

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"

M. Wagner: "Synthese von Stickstoff-Heterocyclen durch enantioselektive Lithiierung"

F. Marr: "Enantiomerenangereicherte, lithiierte S-Allylmonothiocarbamate - Synthese, Eigenschaften und Reaktionsweise"

C. Schultz-Fademrecht: "Chirale Allenylcarbamate - Darstellung und Verwendung in der enantioselektiven Synthese"

M. Brüggemann: "Asymmetrische Totalsynthese von enantiomerenreinem (+)- und (-)-Metachromin A mit chiralen 3-Sulfonyl-1,3-oxazolidinen und Titanenolaten"

M. Seppi: "1-Aryl-1-alkenylcarbamate: Carbolithiierung und enantioselektive g-Deprotonierung zu chiralen Homoenolat-Reagenzien"

M. Özlügedik: "(-)-Spartein-vermittelte enantioselektive Homoaldol-Reaktion cyclischer Allylcarbamate und die

G. Christoph: “Intramolekulare Cyclisierungen mit stannylsubstituierten Alkylcarbamaten Enantioselektiver Aufbau von Carbo- und Heterocyclen“