Enantioselective intramolecular hydroarylation of alkenes via directed C-H bond activation.
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.
Harada
Hitoshi
H
Department of Chemistry, University of California, and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
Thalji
Reema K
RK
Bergman
Robert G
RG
Ellman
Jonathan A
JA
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
D000475:Alkenes; D006844:Hydrocarbons, Cyclic; D007097:Imines; D008024:Ligands; D009943:Organophosphorus Compounds; D017975:Ruthenium Compounds; C434331:phosphoramidite; D002244:Carbon; D006859:Hydrogen; C038365:ruthenium chloride