title: Enantioselective intramolecular hydroarylation of alkenes via directed C-H bond activation.
abstract: Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe)2]2 and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.
authors.affiliation: Department of Chemistry, University of California, and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Harada
authors.forename: Reema K
authors.initials: RK
authors.lastname: Thalji
authors.forename: Robert G
authors.initials: RG
authors.lastname: Bergman
authors.forename: Jonathan A
authors.initials: JA
authors.lastname: Ellman
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007097:Imines / Q000737:chemistry; D007536:Isomerism; D008024:Ligands; D009943:Organophosphorus Compounds / Q000737:chemistry; D017975:Ruthenium Compounds / Q000737:chemistry
chemical_list: D000475:Alkenes; D006844:Hydrocarbons, Cyclic; D007097:Imines; D008024:Ligands; D009943:Organophosphorus Compounds; D017975:Ruthenium Compounds; C434331:phosphoramidite; D002244:Carbon; D006859:Hydrogen; C038365:ruthenium chloride