Ruthenium–Lewis Acid Catalyzed Asymmetric Diels–Alder Reactions between Dienes and α,β-Unsaturated Ketones

Article Article scientifique Article Ruthenium–Lewis Acid Catalyzed Asymmetric Diels–Alder Reactions between Dienes and α,β-Unsaturated Ketones eng 2007 author Rickerby Jenny 628625 author Vallet Martial 538352 author Bernardinelli Gérald Hugues 24765 author Viton Florian 126549 author Kundig Ernst Peter 26401 3354-3368 10.1002/chem.200600851 17226865 0947-6539 The complex [Ru(Cp)(R,R-BIPHOP-F)(acetone)][SbF(6)], (R,R)-1 a, was used as catalyst for asymmetric Diels-Alder reactions between dienes (cyclopentadiene, methylcyclopentadiene, isoprene, 2,3-dimethylbutadiene) and alpha,beta-unsaturated ketones (methyl vinyl ketone (MVK), ethyl vinyl ketone, divinyl ketone, alpha-bromovinyl methyl ketone and alpha-chlorovinyl methyl ketone). The cycloaddition products were obtained in yields of 50-90 % and with enantioselectivities up to 96 % ee. Ethyl vinyl ketone, divinyl ketone and the halogenated vinyl ketones worked best and their reactions with acyclic dienes consistently provided products with >90 % ee. alpha-Chlorovinyl methyl ketone performed better than alpha-bromovinyl methyl ketone. The reaction also provided a [4.3.1]bicyclic ring system in 95 % ee through an intramolecular cycloaddition reaction. Crystal structure determinations of [Ru(Cp)((S,S)-BIPHOP-F)(mvk)][SbF(6)], (S,S)-1 b, and [Ru(Cp)((R,R)-Me(4)BIPHOP-F)(acrolein)][SbF(6)], (R,R)-2 b, provided the basis for a rationalization of the asymmetric induction. Asymmetric catalysis Diels-Alder reactions Dienophiles Lewis acids Ruthenium Dewey 540 36 Département de chimie organique 141 false Chemistry 13 12 1ba29759-47f6-46bd-8459-e7e55a0dd98f Article Restricted file1.pdf 469219 application/pdf restrictedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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Ruthenium–Lewis Acid Catalyzed Asymmetric Diels–Alder Reactions between Dienes and α,β-Unsaturated Ketones	Chemistry			2007	760	8

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Rickerby, Jenny