title: Iridium-Catalyzed Stereoselective Allylic Alkylation Reactions with Crotyl Chloride.
abstract: The development of the first enantio-, diastereo-, and regioselective iridium-catalyzed allylic alkylation reaction of prochiral enolates to form an all-carbon quaternary stereogenic center with an aliphatic-substituted allylic electrophile is disclosed. The reaction proceeds with good to excellent selectivity with a range of substituted tetralone-derived nucleophiles furnishing products bearing a newly formed vicinal tertiary and all-carbon quaternary stereodyad. The utility of this protocol is further demonstrated via a number of synthetically diverse product transformations.
authors.affiliation: The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101-20, Pasadena, CA, 91125, USA.
authors.forename: J Caleb
authors.initials: JC
authors.lastname: Hethcox
authors.affiliation: The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101-20, Pasadena, CA, 91125, USA.
authors.forename: Samantha E
authors.initials: SE
authors.lastname: Shockley
authors.affiliation: The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101-20, Pasadena, CA, 91125, USA.
authors.forename: Brian M
authors.initials: BM
authors.lastname: Stoltz
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D044024:Tetralones / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000475:Alkenes; D000498:Allyl Compounds; D044024:Tetralones; D007495:Iridium; C000628212:crotyl chloride
keywords: allylic alkylation; enantioselective synthesis; iridium; quaternary stereocenter; vicinal stereocenters