title: Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode.
abstract: A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this S(N)1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.
authors.affiliation: Merck Center for Catalysis, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Chun
authors.initials: C
authors.lastname: Liu
authors.affiliation: Merck Center for Catalysis, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: E Zachary
authors.initials: EZ
authors.lastname: Oblak
authors.affiliation: Merck Center for Catalysis, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Mark N
authors.initials: MN
authors.lastname: Vander Wal
authors.affiliation: Merck Center for Catalysis, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Andrew K
authors.initials: AK
authors.lastname: Dilger
authors.affiliation: Merck Center for Catalysis, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Danielle K
authors.initials: DK
authors.lastname: Almstead
authors.affiliation: Merck Center for Catalysis, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: David W C
authors.initials: DW
authors.lastname: MacMillan
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D002412:Cations / Q000737:chemistry; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D002412:Cations; D007211:Indoles; D007659:Ketones; D010100:Oxygen