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Catalysis U sing P hosphorus in M inute Q uantities (ESR 8)

Catalysis U sing P hosphorus in M inute Q uantities (ESR 8). Christian Müller Freie Universität Berlin Institut für Chemie und Biochemie Anorganische Chemie Fabeckstr . 34/36 D-14195 Berlin. Impressions of Berlin. Hahn-Meitner-Bau der Freien Universität.

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Catalysis U sing P hosphorus in M inute Q uantities (ESR 8)

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  1. CatalysisUsingPhosphorus in Minute Quantities (ESR 8) Christian Müller Freie Universität Berlin Institut für Chemie und Biochemie Anorganische Chemie Fabeckstr. 34/36 D-14195 Berlin

  2. Impressions of Berlin Hahn-Meitner-Bau der Freien Universität Institut für Chemie und Biochemie Brandenburger Tor Dom, Spree und Alexanderplatz c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013

  3. B.4.2. Fellows individual researchprojects SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  4. Catalysisusingphosphorus in minutequantities Savingphosphorus… • Highlyactivecatalysts • Highlyselectivecatalysts • Low-costaccess / high yield in synthesis • Modular synthesisofphosphorus-basedligands • New catalyticreactions • Recycling • …. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  5. Phosphorusligandsstudiedat FU Berlin • Low-coordinatephosphorusligands: phosphinines Phosphinine Phosphabarrelene • aromatic, planar, p-acceptingligands • G. Märkl, Angew. Chem. 1966, 78, 907. • G. Märkl, Angew. Chem. Int. Ed. Engl. 1968, 7, 733. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  6. Phosphinines in Catalysis • C. Müller • “Phosphinine Ligands” in Phosphorus Ligand Effects in Homogeneous Catalysis: Design and Synthesis (Ed.: P.C.J. Kamer, P.W.N.M van Leeuwen), Wiley-VCH, 2012. • C. Müller*, D. Vogt • “Phosphinine-Based Ligands in Homogeneous Catalysis: State of the Art and Future Perspectives” inPhosphorus Chemistry: Catalysis and Material Science Applications, Vol. 36 (Ed.: M. Peruzzini, L. Gonsalvi), Chapter 6, Springer, 2011 • C. Müller*, D. Vogt • “Phosphinines as Ligands in Homogeneous Catalysis: Recent Developments, Concepts and Perspectives” • Dalton Trans. 2007, 47, 5505-5523. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  7. Phosphinines in Catalysis • Few examples reported in literature (Zenneck, Le Floch, Breit, Reetz, Müller) • Rh-catalyzed Hydroformylation of (internal) alkenes: isomerization • High activity, low selectivity • B. Breit et al., Chem. Eur. J. 2001, 7, 3106 SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  8. Phosphinines in Catalysis L = • High selectivity towards 2-methyloctanal • J.J.M. Weemers, W.N.P. van der Graaff, E.A. Pidko, M. Lutz, C. Müller, Chem. Eur. J. 2013, accepted for publication. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  9. Phosphinines in Catalysis • Au(I)-Catalysis • F. Heutz, Bachelor thesis, TU/e; unpublished • Ni- and Pd-Catalyzed Suzuki-MiyauraCross-Coupling Reactions • Cooperation with Cyril Godard / Carmen Claver, Tarragona; unpublished SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  10. Phosphabarrelenesin Catalysis • Few examples reported in literature (Le Floch, Breit, Müller) • Rh-catalyzed Hydroformylation of (internal) alkenes: • High activity and selectivity, essentially no isomerization L = B. Breit et al., Chem. Eur. J. 2006, 12, 6930 SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  11. Phosphabarrelenesin Catalysis • Tandem Hydroformylation-CyclizationSequence D N 93% O N CO/H2 Rh/L Nagstatin N L = O N Streptomyces amakusaensis anticancer potential • P.S. Bäuerlein, I. Arenas Gonzalez, J.J.M. Weemers, M. Lutz, A.L. Spek, D. Vogt, C. Müller*, Chem. Commun. 2009, 4944-4946. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  12. Synthesis of Phosphinines: A Modular Approach + Pyrylium salt • G. Märkl, Angew. Chem. 1966, 78, 907. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  13. Synthesis of Phosphinines: A Modular Approach • P(SiMe3)3 (Nieke/Westermann): lowyield (15-30%) • P(CH2OH)3 (Pringle): lowyield (15-30%) • PH3 (Pringle): high yield(Phoscinet STSM JarnoWeemers 2010) (DE 197 43 197 A1, BASF) • PH4I (Märkl, not commericallyavailableanymore): high yield • NaPH2 (Grützmacher): ???? → veryattractive route SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  14. Synthesis of Phosphinines: A Modular Approach • C. R. Chimie2010, 13, 1127. • Tetrahedron Lett. 2006, 47, 2017. • Chem. Eur. J. 2008, 14,8803. • New J. Chem. 2010, 34, 1547. • Organometallics 2008, 27, 834. • Dalton Trans. 2007, 47, 5505. • Chem. Eur. J. 2011, 17, 2510. • Chem. Eur. J. 2008, 14,4899. • Chem. Eur. J. 2007, 13, 4548. • Chem. Eur. J. 2013, accepted. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  15. NovelCoordinationCompoundsBased on Phosphinines • Triplet Emitter • H2O Oxidation • CO2 Hydrogenation • M. Hissler • A. Macchioni • L. Gonsalvi • L.E.E. Broeckx, M. Lutz, D. Vogt, C. MüllerChem. Commun. 2011, 47, 2003-2005 • Microreview: C. Müller, L.E.E. Broeckx, I. de Krom, J.J.M. WeemersEur. J. Inorg. Chem. 2013, 187. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  16. Reactivity Studies • I. de Krom, E.A. Pidko, M. Lutz, C. Müller Chem. Eur. J. 2013, accepted for publication. • I. de Krom, L.E.E. Broeckx, M. Lutz, C. Müller Chem. Eur. J. 2013, 19, 3676. SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  17. Tandem Hydroformylation-Cyclization Sequence CALB T = 40°C Toluene 3 d -S- -R- • J.J.M. Weemers, F.D. Sypaseuth, C. Müller, to be submitted SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  18. Tandem Hydroformylation-Cyclization Sequence 31P NMR 114.8ppm -R- -R- • J.J.M. Weemers, F.D. Sypaseuth, C. Müller, to be submitted SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  19. Tandem Hydroformylation-Cyclization Sequence 31P NMR 105.4 ppm Own work Crabtree (1979) Pfaltz (2000) Andersson (2007) • Analogy to cationic Ir-catalysts for the (asymmetric) hydrogenation of “difficult” substrates SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  20. Tandem Hydroformylation-Cyclization Sequence ee > 95% (S) Gasuptake Curve: Activity 96% conversion (44 h) TOF = 12.5 h-1 Vtot= 8 mL, cIr= 5 mM, Ir:L:S= 1:1.05:50, T= 25°C, p= 10 bar H2 • J.J.M. Weemers, F.D. Sypaseuth, C. Müller, to be submitted SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

  21. Acknowledgements SUSPHOS Kick-off-meeting, Regensburg, 18.03.2013 c.mueller@fu-berlin.de; www.bcp.fu-berlin/ak-mueller

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