Sequential olefin metathesis – Intramolecular asymmetric Heck reactions in the synthesis of polycycles

Lautens, Mark; Zunic, Valentin
February 2004
Canadian Journal of Chemistry;Feb2004, Vol. 82 Issue 2, p399
Academic Journal
Application of the intramolecular asymmetric Heck reaction in the desymmetrization of a novel class of symmetrical bicyclodienes, synthesized through a diastereoselective double ring-closing metathesis (DSRCM) reaction, was achieved with good yields (approximately 80%) and excellent enantioselectivities (up to 99% ee). Three contiguous stereocenters are established in a single desymmetrization reaction. The use of thallium carbonate as base in the asymmetric Heck reaction favours double bond migration in 13. Cationic conditions delivered products with good to excellent enantioselectivities, surpassing the results under neutral conditions.


Related Articles

  • Application of Olefin Cross-Metathesis to the Synthesis of Biologically Active Natural Products. Prunet, Joelle // Current Topics in Medicinal Chemistry;Nov2005, Vol. 5 Issue 15, p1559 

    An overview of the use of olefin cross-metathesis in the synthesis of biologically active natural products is presented. The diverse examples are organized according to the outcome of the olefin constructed by the cross-metathesis reaction: this olefin can be either present in the final product,...

  • The Application of Olefin Metathesis to the Synthesis of Biologically Active Macrocyclic Agents. van de Weghe, Pierre; Eustache, Jacques // Current Topics in Medicinal Chemistry;Nov2005, Vol. 5 Issue 15, p1495 

    Recent developments of the metathesis reaction in the area of biologically active molecules are presented. Scope and limitations of ring-closing metathesis to form medium and large rings are discussed and illustrated by the epothilone synthesis. Applications of the metathesis reaction related to...

  • Chemical transformations of cis-W(CO)4(C5H5N)2 in the ring-opening metathesis polymerization of norbornene. Bencze, L.; B�r�, N.; Szab�-Ravasz, B.; Mihichuk, L. // Canadian Journal of Chemistry;Apr2004, Vol. 82 Issue 4, p499 

    The six-coordinate W0 complex cis-W(CO)4(C5H5N)2 has been found to be active in the in situ formation of a carbene species from norbornene, which generates a typical ring-opening metathesis product (ROMP). A proposed mechanism of initiation suggests that the reaction involves a 2,3-hydrogen...

  • Dynamic Chemical Counting of Active Centers of Molybdena—Alumina Metathesis Catalysts. Handzlik, Jarosáaw; Ogonowski, Jan // Catalysis Letters;Jun2003, Vol. 88 Issue 3/4, p119 

    A dynamic method of chemical counting of active centers of alkene metathesis is proposed and applied to study MoO3/Al2O3 and MoO3/Al2O3-SnMe4 systems. For the MoO3/Al2O3 catalyst, the estimated number of the active sites is less than 1% of the total number of the Mo atoms. MoO3/Al2O3-SnMe4...

  • Olefin Metathesis Route to Antiviral Nucleosides. Agrofoglio, Luigi A.; Nolan, Steven P. // Current Topics in Medicinal Chemistry;Nov2005, Vol. 5 Issue 15, p1541 

    The success of the early nucleoside agents, the toxicity and metabolic instability of many nucleoside analogues and the effects of viral pathogens on public health are driving the design, synthesis and evaluation of new nucleoside analogues. In this context, a powerful reaction has emerged over...

  • Inside the black box � Perspectives on transformations in catalysis. Fogg, Deryn E. // Canadian Journal of Chemistry;Oct2008, Vol. 86 Issue 10, p931 

    Tandem catalysis and olefin metathesis are powerful tools in the development of sustainable synthetic practices. This Award Lecture describes our advances in designing new tandem metathesis-hydrogenation methodologies for the synthesis of �designer materials� and Ru-pseudohalide...

  • Cross-dressing proteins by olefin metathesis. Kirshenbaum, Kent; Arora, Paramjit S. // Nature Chemical Biology;Sep2008, Vol. 4 Issue 9, p527 

    The article discusses the process of cross-dressing of proteins using olefin metathesis. It offers an overview of how modifications in protein structure can be made possible through metathesis catalysts and cites the study conducted by Benjamin G. Davis and his colleagues that describe the...

  • Catalytic Z-selective olefin cross-metathesis for natural product synthesis. Meek, Simon J.; O'Brien, Robert V.; Llaveria, Josep; Schrock, Richard R.; Hoveyda, Amir H. // Nature;3/24/2011, Vol. 471 Issue 7339, p461 

    Alkenes are found in many biologically active molecules, and there are a large number of chemical transformations in which alkenes act as the reactants or products (or both) of the reaction. Many alkenes exist as either the E or the higher-energy Z stereoisomer. Catalytic procedures for the...

  • The Synthesis of 5-, 6-, 7- and 8-Membered Oxygen-containing Benzo-fused Rings using Alkene Isomerization and Ring-closing Metathesis Reactions. Pathak, Rakhi; Panayides, Jenny-Lee; Jeftic, Tanya D.; De Koning, Charles B.; Van Otterlo, Willem A. L. // South African Journal of Chemistry;2007, Vol. 60, p1 

    A number of benzo-fused oxygen-containing heterocycles were synthesized from allyl-3-isopropoxy-4-methoxybenzaldehyde using metathesis or an alkene isomerization-metathesis sequence as key synthetic steps. Benzo-fused compounds thus formed included a 3,6-dihydro-1H-2-benzoxocine,...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics