Intramolecular Pd-Catalyzed Carbocyclization, Heck Reactions, and Aryl-Radical Cyclizations with Planar Chiral Arene Tricarbonyl Chromium Complexes
journal contributionposted on 08.02.2001, 00:00 by E. Peter Kündig, Hassen Ratni, Benoît Crousse, Gérald Bernardinelli
(o-butenylhalobenzene)Cr(CO)3 complexes were synthesized by diastereoselectve allylmetal additions to o-halo benzaldehyde complexes. The addition of allylZnBr proved particularly convenient and clean. The complexes undergo intramolecular Pd-catalyzed cyclizations (Heck reactions) without decomplexation and/or alkene isomerization. In complexes with a benzylic stereogenic center, the diastereoselectivity of the alkene carbopalladation is governed by the planar chirality of the complex rather than by the benzylic stereogenic center in the side chain. This reaction outcome can be rationalized by the geometry of the arene plane vs that of the Pd coordination plane in the transition step of the alkene carbopalladation step. An alternative cyclization procedure involves the generation of a Cr(CO)3-coordinated arene radical from the bromo and iodo complexes. Intramolecular aryl-radical cyclization affords indan complexes. The transition metal arene π-bond remains intact during this process.
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Heck reactionsalternative cyclization procedurebenzylic stereogenic centertransition stepside chainPlanar Chiral Arene Tricarbonyl Chromium ComplexesHeck Reactionsindan complexesalkene carbopalladation stepalkene carbopalladationreaction outcomePd coordination planediastereoselectve allylmetal additionshalo benzaldehyde complexesarene plane vsiodo complexes