Ulm, - ... Cyclizations onto acyclic alkenes Axially chiral induction Cascade cyclization 6-exo-cyclization

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  • Ulm,

  • Pd catalysts

    PdCl2(dppf)

    Pd2dba3

    Pd(PPh3)4

  • Negishi-coupling

  • Yong Yu, Andrew D. Bond, Philip W. Leonard, Ulrich J. Lorenz, Tatiana V. Timofeeva, K. Peter C. Vollhardt, Glenn D. Whitener and Andrey A. Yakovenko (2006). "Hexaferrocenylbenzene". Chem. Commun. (24): 2572–2574.

    http://en.wikipedia.org/wiki/Chem._Commun. http://en.wikipedia.org/wiki/Chem._Commun.

  • Negishi is better than Stille

  • The ZACA-ReactionZirconium-catalyzed asymmetric carboalumination

  • Liang, B.; Negishi, Ei-ichi. Highly Efficient Asymmetric Synthesis of Fluvirucinine A1 via Zr-Catalyzed Asymmetric Carboalumination of Alkenes (ZACA)-Lipase- Catalyzed Acetylation Tandem Process. Org. Lett. 2008, 10(2),193-195.

  • Motuporin-dimethyl-diester

    1,3-Dienes from Alkyne and Vinyliodide

  • Synthesis of linear terpenes

    Review: Negishi,E.; Hu, Q.; Huang, Z.; Quian, M.; Wang, G. Aldrichimica Acta 2005, 38, 71.

  • Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis Sambasivarao Kotha, Kakali Lahiri and Dhurke Kashinath Tetrahedron 2002, 48, 9633-9695

    Suzuki-Miyaura-cross coupling

    http://en.wikipedia.org/wiki/Tetrahedron http://en.wikipedia.org/wiki/Tetrahedron

  • Synthesis of B2pin2

  • Pd[PPh3)]4

    BBr3

  • Epothilones A (R =H= and B (R= Me)

    Danishefsky, S. J. et al, Angew. Chem., Int. Ed. Eng. 1997, 36(7), 757-759

  • Stille CC Cross Coupling

  • Rate of ligand transfer (transmetalation) from tin: alkynyl > alkenyl > aryl > allyl = benzyl > α-alkoxyalkyl > alkyl

    P. Espinet, A. M. Echavarren (2004). "The Mechanisms of the Stille Reaction". Angew. Chem. Int. Ed. 43 (36): 4704– 4734.

    http://en.wikipedia.org/wiki/Angewandte_Chemie_International_Edition http://en.wikipedia.org/wiki/Angewandte_Chemie_International_Edition

  • Intramolecular Stille coupling

  • Kumada-Corriu Cross Coupling

  • A Kumada coupling or Kumada-Corriu coupling is a cross coupling reaction in organic chemistry between an alkyl or aryl Grignard reagent and an aryl or vinyl halocarbon catalysed by nickel or palladium. This reaction is relevant to organic synthesis because it gives access to styrene derivatives. The reaction type was reported independently by two groups in 1972, and was named after Makoto Kumada. The reaction forshadowed many related metal-catalyzed coupling reactions, such as the Sonogashira coupling and the Suzuki coupling.

    http://en.wikipedia.org/wiki/Cross_coupling_reaction http://en.wikipedia.org/wiki/Cross_coupling_reaction http://en.wikipedia.org/wiki/Cross_coupling_reaction http://en.wikipedia.org/wiki/Cross_coupling_reaction http://en.wikipedia.org/wiki/Organic_chemistry http://en.wikipedia.org/wiki/Organic_chemistry http://en.wikipedia.org/wiki/Alkyl http://en.wikipedia.org/wiki/Alkyl http://en.wikipedia.org/wiki/Aryl http://en.wikipedia.org/wiki/Aryl http://en.wikipedia.org/wiki/Grignard_reagent http://en.wikipedia.org/wiki/Grignard_reagent http://en.wikipedia.org/wiki/Aryl http://en.wikipedia.org/wiki/Aryl http://en.wikipedia.org/wiki/Vinyl http://en.wikipedia.org/wiki/Vinyl http://en.wikipedia.org/wiki/Halocarbon http://en.wikipedia.org/wiki/Halocarbon http://en.wikipedia.org/wiki/Nickel http://en.wikipedia.org/wiki/Nickel http://en.wikipedia.org/wiki/Palladium http://en.wikipedia.org/wiki/Palladium http://en.wikipedia.org/wiki/Organic_synthesis http://en.wikipedia.org/wiki/Organic_synthesis http://en.wikipedia.org/wiki/Organic_synthesis http://en.wikipedia.org/wiki/Organic_synthesis http://en.wikipedia.org/wiki/Styrene http://en.wikipedia.org/wiki/Styrene http://en.wikipedia.org/wiki/Makoto_Kumada http://en.wikipedia.org/wiki/Makoto_Kumada http://en.wikipedia.org/wiki/Sonogashira_coupling http://en.wikipedia.org/wiki/Sonogashira_coupling http://en.wikipedia.org/wiki/Suzuki_coupling http://en.wikipedia.org/wiki/Suzuki_coupling

  • Buchwald-Hartwig CN-Coupling

  • John P. Wolfe and Stephen L. Buchwald „Org. Synth 2004, Coll. Vol. 10: 423

    http://en.wikipedia.org/wiki/Organic_Syntheses http://en.wikipedia.org/wiki/Organic_Syntheses http://en.wikipedia.org/wiki/Organic_Syntheses http://en.wikipedia.org/wiki/Organic_Syntheses

  • Sonogashira-Castro-Reaction

    Sonogashira, K.; Tohda, Y.; Hagahira, N. Tetrahedron Lett. 1975, 50, 4467

  • Heck Reaction

    Is not a CC-coupling but olefin addition elimination process

  • Catalytic cycle of the Heck reaction

  • Stereo- and Regiochemistry

  • Formation of bridged rings

  • Bridged rings in natural products synthesis

  • Fused rings in natural products synthesis

  • Formation of spirocycles by 6-exo-attack

  • Double spirocyclization

  • Bicyclic alkenes

  • Cyclizations onto acyclic alkenes

  • Axially chiral induction

  • Cascade cyclization

  • 6-exo-cyclization

  • Cascade reaction

  • Cyclizations onto exocyclic olefins: eclipsed boat transition state

  • 6-exo onto seven-membered ring

  • 6-exo with stereogenic center outside the tether

  • 7-exo cyclization

  • Asymmetric version

  • Chiral phosphines

  • Enantiotopos selectivity

  • Synthesis of polyketides

  • Alkaloids

  • Rhazinilam

  • Gu, Z.; Zakarian, A. Org. Lett. 2010,12, 4224-4227

  • References Heck-reaction (1) (a) Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jpn. 1971, 44, 581. (b) Heck, R. F.; Nolley, J. P., Jr. J. Org. Chem. 1972, 37, 2320. (2) Selected reviews include: (a) de Meijere, A.; Meyer, F. E. Angew. Chem., Int. Ed. Engl. 1994, 33, 2379. (b) Bräse, S.; de Meijere, A. In Metal-Catalyzed Cross Coupling Reactions; Stang, P. J., Diederick, F., Eds; Wiley-VCH: Weinheim, 1998; Chapter 3. (c) Link, J. T.; Overman, L. E. In Metal-Catalyzed Cross Coupling Reactions; Stang, P. J., Diederick, F., Eds; Wiley-VCH: Weinheim, 1998; Chapter 6. (d) Link, J. T. Organic Reactions; Wiley: Hoboken, NJ, 2002; Vol. 60, Chapter 2. (3) For recent reviews of the asymmetric Heck reaction, see: (a) Shibasaki, M.; Vogl, E. M. J. Organomet. Chem. 1999, 1. (b) Donde, Y.; Overman, L. E. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley-VCH: New York, 2000; Chapter 8G. (4) Dounay, A. B.; Overman, L. E. Chem. Rev. 2003, 103, 2945.

  • Carbocyclization with Pd