title: Intramolecular Tsuji-Trost-type Allylation of Carboxylic Acids: Asymmetric Synthesis of Highly π-Allyl Donative Lactones.
abstract: Tsuji-Trost-type asymmetric allylation of carboxylic acids has been realized by using a cationic CpRu complex with an axially chiral picolinic acid-type ligand (Cl-Naph-PyCOOH: naph = naphthyl, py = pyridine). The carboxylic acid and allylic alcohol intramolecularly condense by the liberation of water without stoichiometric activation of either nucleophile or electrophile part, thereby attaining high atom- and step-economy, and low E factor. This success can be ascribed to the higher reactivity of allylic alcohols as compared with the allyl ester products in soft Ru/hard Brønstead acid combined catalysis, which can function under slightly acidic conditions unlike the traditional Pd-catalyzed system. Detailed analysis of the stereochemical outcome of the reaction using an enantiomerically enriched D-labeled substrate provides an intriguing view of enantioselection.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Suzuki
authors.affiliation: Graduate School of Pharmaceutical Sciences, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Seki
authors.affiliation: Graduate School of Pharmaceutical Sciences, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Shinji
authors.initials: S
authors.lastname: Tanaka
authors.affiliation: Graduate School of Pharmaceutical Sciences, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Masato
authors.initials: M
authors.lastname: Kitamura
mesh_terms: D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry
chemical_list: D000498:Allyl Compounds; D002264:Carboxylic Acids; D007783:Lactones; D009942:Organometallic Compounds; D012428:Ruthenium