title: Pd(II)-catalyzed hydroxyl-directed C-H olefination enabled by monoprotected amino acid ligands.
abstract: A novel Pd(II)-catalyzed ortho-C-H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle.
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
authors.forename: Yi
authors.initials: Y
authors.lastname: Lu
authors.forename: Dong-Hui
authors.initials: DH
authors.lastname: Wang
authors.forename: Keary M
authors.initials: KM
authors.lastname: Engle
authors.forename: Jin-Quan
authors.initials: JQ
authors.lastname: Yu
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry*; D008024:Ligands; D010165:Palladium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000596:Amino Acids; D006878:Hydroxides; D008024:Ligands; D010165:Palladium; D002244:Carbon; D006859:Hydrogen; C031356:hydroxide ion