title: Catalytic asymmetric synthesis of sterically hindered tertiary α-aryl ketones.
abstract: The catalytic asymmetric synthesis of a series of tertiary α-aryl cyclopentanones and cyclohexanones has been accomplished via a Pd-catalyzed decarboxylative protonation of the corresponding α-aryl-β-keto allyl esters. Enantioselectivities of up to 92% ee and 74% ee were achieved for cyclopentanone and cyclohexanone substrates, respectively. The route described gives access to these important structural motifs in moderate to high levels of enantioselectivity. In particular, this is only the second direct approach for the preparation of tertiary α-aryl cyclopentanones. The synthetic approach allows for simple modification of the aryl group. Significantly, substrates containing sterically hindered aryl groups gave the highest levels of enantioselectivity, and these aryl groups were readily installed by a Pb-mediated arylation of a β-keto allyl ester.
authors.affiliation: Centre for Synthesis and Chemical Biology, School of Chemistry and Chemical Biology, University College Dublin , Belfield, Dublin 4, Ireland.
authors.forename: Robert
authors.initials: R
authors.lastname: Doran
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Guiry
mesh_terms: D002384:Catalysis; D003512:Cyclohexanones / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D004952:Esters; D006865:Hydrogenation; D007659:Ketones / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D003512:Cyclohexanones; D003517:Cyclopentanes; D004952:Esters; D007659:Ketones; C007201:cyclopentanone