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Enantioselective catalytic diels-alder reactions with enones as dienophiles

AuthorsCarmona, Daniel ; Viguri, Fernando ; Asenjo, Ainara ; Lahoz, Fernando J. ; García-Orduña, P. ; Oro, Luis A.
Issue Date2012
PublisherAmerican Chemical Society
CitationOrganometallics 31(12): 4551-4557 (2012)
AbstractThe aqua complexes (S M,R C)-[(η 5-C 5Me 5)M(PROPHOS)(H 2O)][SbF 6] 2 [PROPHOS = (R)-propane-1,2-diylbis(diphenylphosphane); M = Rh (1), Ir (2)] are active catalysts for the asymmetric Diels-Alder reaction between ketones and dienes. At low temperatures, enantioselectivities of up to 89% ee are achieved. The intermediate Lewis acid-dienophile complexes (S M,R C)-[(η 5-C 5Me 5)M(PROPHOS)(MVK)][SbF 6] 2 (MVK = methyl vinyl ketone; M = Rh (3), Ir (4)) and (S Ir,R C)- [(η 5-C 5Me 5)Ir(PROPHOS)(EVK)][SbF 6] 2 (EVK = ethyl vinyl ketone (5)) have been isolated and characterized by analytical and spectroscopic means, including the determination of the crystal structure of the iridium complexes 4 and 5 by X-ray diffractometric methods. Structural parameters indicate that the dispositions of the coordinated dienophiles are controlled by the CH/π attractive interactions established between a phenyl group of the PROPHOS ligand and the α-vinyl proton of the ketones. Proton NMR parameters indicate that these interactions are maintained in solution. From these data, the stereoselectivity of the catalytic reaction is discussed. © 2012 American Chemical Society.
Identifiersdoi: 10.1021/om300346s
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ISQCH) Artículos
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