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Novel P-Stereogenic Bidentate Phosphorus Ligands for Asymmetric Catalysis

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Novel P-Stereogenic Bidentate Phosphorus Ligands for Asymmetric Catalysis Novel P-Stereogenic Bidentate Phosphorus Ligands for Asymmetric Catalysis Von der Naturwissenschaftlichen Fakultät der Gottfried Wilhelm Leibniz Universität Hannover zur Erlangung des Grades eines Doktors der Naturwissenschaften Dr. rer. nat. – genehmigte Dissertation von M. Sc. Nikolai Vinokurov geboren am 10.03.1980, in Krasnodar, Russland 2007 Referent: Prof. Dr. H. Butenschön Korreferent: Prof. Dr. H. Duddeck Tag der Promotion 21. 11. 2007 ZUSAMMENFASSUNG Neue P-chirale zweizähnige Phosphanliganden für die Asymmetrische Katalyse Heutzutage werden P-chirale Diphosphane für eine Vielzahl asymmetrischer Übergangsmetall-katalysierter Reaktionen wie Hydrierungen, Hydrosilylierungen, Alkylierungen, C-C-Kupplungsreaktionen und Isomerisierungen häufig angewandt. Die Synthesewege zu P-chiralen zweizähnigen Liganden beschränken sich jedoch auf nur wenige Beispiele, weil die Synthese P-chiraler Verbindungen oft als problematisch gilt. Im Rahmen dieser Dissertation wurden neue Wege zu P-chiralen Diphosphanliganden beschrieben, um danach deren erste Anwendungen in der asymmetrischen Katalyse aufzuzeigen. Die Ru-katalysierte Homo-Metathese von P-chiralem (Sp)-Methylphenylvinylphosphanoxid wurde in Gegenwart moderner Alkenmetathese-Katalysatoren durchgeführt. Anschließend wurde das P-chirale trans-1,2-Diphosphanyldioxid als Dienophil in einer asymmetrischen Diels-Alder-Reaktion mit Cyclopentadien und als Dipolarophil in einer asymmetrischen Huisgen-Cycloaddition mit acyclischen Nitronen eingesetzt, um die ersten P-chiralen Diphosphandioxide mit zwei asymmetrischen Phosphoratomen und einem starren Rückgrat zu erhalten. Die Reduktion dieser neuen P-chiralen Diphosphandioxide durch die Umsetzung mit Ti(OiPr)4/Polymethylhydrosiloxan (PMHS) in THF verläuft unter Erhalt der Konfiguration in hohen Ausbeuten. Die Synthese eines Rhodiumkomplexes mit den neuen P-chiralen Diphosphanen als Liganden konnte auch realisiert werden. Die asymmetrische Pd-katalysierte allylische Alkylierung von 1,3-Diphenyl-2-propenylacetat mit Dimethylmalonat lieferte ein erstes noch nicht optimiertes Ergebnis, indem das gewünschte Produkt in 97% Ausbeute und in einem Enantiomerenüberschuss von 81% vorlag. Darüber hinaus ist es gelungen, einen neuen bimetallischen Ruthenium Präkatalysator für die Alken-Metathese herzustellen. Der Katalysator weist eine elektronenziehende Tricarbonylchromgruppe auf, welche am Benzylidenliganden koordiniert ist. Die katalytischen Eigenschaften dieses neuen Präkatalysators wurden in Ringschluss-, Enin-, Kreuz-, und Homo-Metathesen getestet. Aus den vorliegenden Ergebnissen ist zu schließen, dass der neue Katalysator eine vergleichbare Aktivität wie andere Alken- Metathesekatalysatoren besitzt und diese in manchen Fällen sogar übersteigt. P-Chirale Vinylphosphanoxide · Homodimerisierung · Alken-Metathese · Ruthenium · Asymmetrische Cycloaddition · P-Chirale Diphosphane · Asymmetrische Katalyse · Rhodium ABSTRACT Novel P-Stereogenic Bidentate Phosphorus Ligands for Asymmetric Catalysis Nowadays, P-stereogenic diphosphines are frequently employed in a variety of asymmetric transition metal catalyzed reactions such as hydrogenation, hydrosilylation, alkylation, C-C coupling reactions and isomerization. However, P-chiral diphosphine ligands were less investigated since the synthesis of highly enantiomerically enriched P-stereogenic phosphines often proves to be difficult. This work is devoted to the synthesis of novel P-stereogenic diphosphines for asymmetric catalysis. The target of this project consists of the synthesis of new P-stereogenic diphosphines from P-chiral diphosphine dioxides and their first applications in asymmetric catalysis. The P-chiral (Sp)-methylphenylvinylphosphine oxide was successfully homodimerized in the presence of modern olefin metathesis catalysts. After homo cross-coupling the P-chiral trans- 1,2-diphosphinylethene dioxide was used as a dienophile for an asymmetric Diels-Alder cycloaddition with cyclopentadiene and as a dipolarophile for asymmetric Huisgen cycloaddition with acylic nitrones to access novel P-chiral diphosphine dioxides bearing two asymmetric phosphorus atoms located close to the rigid chiral backbone. The novel P-stereogenic diphosphine dioxides were successfully reduced by the use of Ti(OiPr)4/polymethylhydrosiloxane (PMHS) in THF with complete retention of configuration leading to diastereomerically pure P-chiral diphosphines in high yields. The rhodium complex of a new P-chiral diphosphine could also be synthesized. The novel P-stereogenic diphosphine was employed in the enantioselective Pd-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethylmalonate leading as a first unoptimized result to 97 % yield and 81 % ee of the desired product In addition, a new highly efficient bimetallic ruthenium precatalyst for alkene metathesis was synthesized, in which the benzylidene ligand has been coordinated to a highly electron withdrawing tricarbonylchromium moiety. Screening of the catalytic properties shows that the activity of the new catalyst in ring closing, enyne, cross, and homo-metathesis of alkenes is comparable to and in some cases better than that of known catalysts. P-Chiral Vinylphosphine Oxides · Homodimerization · Alkene Metathesis · Ruthenium · Asymmetric Cycloaddition · P-Stereogenic Diphosphines · Asymmetric Catalysis · Rhodium Die vorliegende Arbeit wurde unter der Leitung von Herrn Prof. Dr. Holger Butenschön in der Zeit von September 2003 bis Juli 2007 am Institut für Chemie der Leibniz Universität Hannover angefertigt. Herrn Prof. Dr. Holger Butenschön danke ich für die Überlassung des interessanten Themas, die hervorragenden Arbeitsbedingungen, die stets freundliche Unterstützung, die Bereitschaft jederzeit für die aufschlussreichen wissenschaftlichen Disskussionen sowie die gute Betreuung herzlich. Meinen herzlichen Dank möchte ich der Gottlieb Daimler- und Karl Benz Stiftung für die Verleihung des Promotionsstipendiums aussprechen. Herrn Prof. Dr. Helmut Duddeck danke ich für die Übernahme des Koreferats. Meinen ehemaligen und jetztigen Kollegen Herrn Dr. Jose Garabatos, Herrn Dr. Mazhar Hussain, Frau Dr. Zhirong Zhao, Frau Dipl.-Chem. Bianka Muschalek, Frau Dipl.-Chem. Karin Kirleis, Herrn Dipl.-Chem. Ingmar Baumgardt, Herrn Dipl.-Chem. Marc Vollmann, Frau Dipl.-Chem. Stephanie Kohser, Herrn Dipl.-Chem. Jingxiang Ma, Herrn M. Sc. Osama Habib, Herrn Dr. Tamer Ezzat, Herrn Dipl.-Chem. Björn Kühn gilt mein Dank für die gute Zusammenarbeit, die ständige Hilfsbereitschaft und die unvergesslichen interessanten Diskussionen. Frau Annette Kandil danke ich für die Hilfe bei organisatorischen Problemen. Mein großes Dankeschön gilt den Mitarbeitern der instrumentalanalytischen Abteilung Dr. D. Albert, Frau D. Körtje, Frau M. Rettstadt, Herrn R. Nöthel, Herrn Dipl.-Chem. M. Astratov, Herrn J. Küster für die schnelle Messungen der NMR- und Massenspektren empfindlicher Substanzen. Herrn Dr. M. Wiebcke und Herrn Dr. R. Wartchow danke ich für die Anfertigung aller Kristallstrukturanalysen. Herrn Dipl.-Chem. Ingmar Baumgardt danke ich für sein ständiges Verständnis! Nicht vergessen möchte ich, allen Mietgliedern der Arbeitskreise Duddeck, Boysen, Hoffmann, Winterfeldt, Dräger, Kirschning und Kalesse für ihre Unterstützung zu danken. Bedanken möchte ich bei meinen ehemaligen Kollegen Herrn Dr. Andriy Stelmakh (AK Kalesse) und Herrn Dr. J. Garabatos, die mir während meiner Arbeit mit Rat und Tat bei Seite gestanden haben. Der Deutschen Forschugsgemeinschaft (DFG) gilt mein besonderer Dank für die Vergabe einer Stelle als wissenschaftlicher Mitarbeiter in Rahmen eines DFG-Projektes. Bei Herrn Vladimir Lusin bedanke ich mich für seine stetige moralische Unterstützung! Svetlana danke ich für Ihre Liebe und moralische Unterstützung! Bei meinen geliebten Eltern möchte ich mich für Ihre große Unterstützung bedanken! Meinen lieben Eltern Valentina und Anatoliy Vinokurov gewidmet ɉɨɫɜɹɳɚɟɬɫɹɆɨɢɦȾɨɪɨɝɢɦɊɨɞɢɬɟɥɹɦ-ȼɚɥɟɧɬɢɧɟɢȺɧɚɬɨɥɢɸȼɢɧɨɤɭɪɨɜɵɦ ABBREVIATIONS D [Į] 20°C Specific Rotation Å Angstrom aq. Aqueous Ar Ar ATR Attenuated Total Reflection Bn Benzyl br broad (NMR) B. p. Boiling Point Bu Butyl t-Bu tert-Butyl c Concentration ºC Degrees Celsius calcd. Calculated cat. Catalyst CM Cross-Metathesis cm–1 Wavenumber 13C NMR 13 C Nuclear Magnetic Resonance į Chemical Shift d Doublet DBTA Dibenzoyltartaric acid dd Doublet of Doublets dr Diastereomeric Ratio de Diastereomeric Excess decomp. Decomposition ee Enantiomeric Excess EI Electronic Impact (Mass Spectrometry) equiv. Equivalent(s) Et Ethyl Fc Ferrocene g gramm GC Gas Chromatography h hour (s) 1H NMR 1H Nuclear Magnetic Resonance HRMS High-resolution Mass Spectroscopy Hz Hertz IR Infrared J Coupling Costant (NMR Spectroscopy) m Multiplet M Molar M+ Parent Molecular Cation Me Methyl Men Menthyl MHz Megahertz mL Milliliter(s) min Minutes mmol Millimol M. p. Melting Point MS Mass Spectrometry m /z Mass-to-charge Ratio (Mass spectrometry) NHC N-heterocylic NMR Nuclear Magnetic Resonance Nu Nucleophile PE Petroleum Ether Ph Phenyl Ppm Part(s) per Million i-Pr Isopropyl PMHS Polymethylhexasiloxane 31P NMR 31P Nuclear Magnetic Resonance rac Racemic RCM Ring-Closing Metathesis s Singlet TBME tert-Butylmethyl Ether THF Tetrahydrofuran t Triplet TLC Thin-layer Chromatography Table of Contents 1 Introduction 1 1.1 Optically Active Phosphorus Ligands: A Historical Overview 1 1.2 Synthesis of P-Chiral Diphosphine Ligands via Their Dioxides and Sulfides 4 1.3 Synthesis of P- Stereogenic Diphosphine Ligands From Phosphine-Boranes 8 1.4 Asymmetric
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