title: Iridium-Catalyzed Enantioselective Allylic Substitution of Enol Silanes from Vinylogous Esters and Amides.
abstract: The enol silanes of vinylogous esters and amides are classic dienes for Diels-Alder reactions. Here, we report their reactivity as nucleophiles in Ir-catalyzed, enantioselective allylic substitution reactions. A variety of allylic carbonates react with these nucleophiles to give allylated products in good yields with high enantioselectivities and excellent branched-to-linear ratios. These reactions occur with KF or alkoxide as the additive, but mechanistic studies suggest that these additives do not activate the enol silanes. Instead, they serve as bases to promote the cyclometalation to generate the active Ir catalyst. The carbonate anion, which was generated from the oxidative addition of the allylic carbonate, likely activates the enol silanes to trigger their activity as nucleophiles for reactions with the allyliridium electrophile. The synthetic utility of this method was illustrated by the synthesis of the anti-muscarinic drug, fesoterodine.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Ming
authors.initials: M
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
mesh_terms: D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D000577:Amides / Q000737:chemistry*; D001559:Benzhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D018727:Muscarinic Antagonists / Q000138:chemical synthesis / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D000577:Amides; D001559:Benzhydryl Compounds; D004952:Esters; D018727:Muscarinic Antagonists; D009942:Organometallic Compounds; D012821:Silanes; D007495:Iridium; C526675:fesoterodine