English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Cationic Ruthenium Allenylidene Complexes as Catalysts for Ring Closing Olefin Metathesis

MPS-Authors
/persons/resource/persons58380

Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons135561

Liebl,  Monika
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58744

Lehmann,  Christian W.
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

External Ressource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Fürstner, A., Liebl, M., Lehmann, C. W., Picquet, M., Kunz, R., Bruneau, C., et al. (2000). Cationic Ruthenium Allenylidene Complexes as Catalysts for Ring Closing Olefin Metathesis. Chemistry - A European Journal, 6(10), 1847-1857. doi:10.1002/(SICI)1521-3765(20000515)6:10<1847:AID-CHEM1847>3.0.CO;2-1.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-3BFA-F
Abstract
A series of well accessible cationic ruthenium allenylidene complexes of the general type [(η6-arene)(R3P)RuCl(=C=C=CR′2)]+ X is described which constitute a new class of pre-catalysts for ring closing olefin metathesis reactions (RCM) and provide an unprecedented example for the involvement of metal allenylidenes in catalysis. They effect the cyclization of various functionalized dienes and enynes with good to excellent yields and show a great tolerance towards an array of functional groups. Systematic variations of their basic structural motif have provided insights into the essential parameters responsible for catalytic activity which can be enhanced further by addition of Lewis or Brønsted acids, by irradiation with UV light, or by the adequate choice of the “non-coordinating” counterion X. The latter turned out to play a particularly important role in determining the rate and selectivity of the reaction. A similarly pronounced influence is exerted by remote substituents on the allenylidene residue which indicates that this ligand (or a ligand derived thereof) may remain attached to the metal throughout the catalytic process. X-ray crystal structures of the catalytically active allenylidene complexes 3 b⋅PF6 and 15⋅OTf as well as of the chelate complex 10 required for the preparation of the latter catalyst are reported.