title: Enantio- and Diastereoselective Dehydrative "One-Step" Construction of Spirocarbocycles via a Ru/H+-Catalyzed Tsuji-Trost Approach.
abstract: Chiral spirocarbocyclic skeletons are ubiquitous in natural products. An intramolecular Tsuji-Trost (T-T) α-allylation of simple cyclic ketones is a reasonable approach to construct chiral spriocarbocyclic motifs; however, it has been a challenging approach despite many excellent intermolecular examples. For the first time, this has been achieved by a Ru/H+combined catalyst that dehydratively cyclizes racemic allylic alcohols comprising a simple ketone via simultaneous activation of the C=O and OH groups. This chiral technology facilitates the construction of various spirocarbocycles containing two contiguous spiro all-carbon quaternary and tertiary stereocenters. Among four possible stereoisomers, one stereoisomer can be selectively produced in high yield, enhancing the feasibility of the T-T strategy, particularly in the synthesis of spirocarbocycles.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya, 464-8601, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Suzuki
authors.affiliation: Research Center for Materials Science, Nagoya University, Chikusa, Nagoya, 464-8602, Japan.
authors.forename: Namdev
authors.initials: N
authors.lastname: Vatmurge
authors.affiliation: Research Center for Materials Science, Nagoya University, Chikusa, Nagoya, 464-8602, Japan.
authors.forename: Shinji
authors.initials: S
authors.lastname: Tanaka
authors.affiliation: Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya, 464-8601, Japan.
authors.forename: Masato
authors.initials: M
authors.lastname: Kitamura
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D015394:Molecular Structure; D012428:Ruthenium / Q000737:chemistry*; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D056831:Coordination Complexes; D006571:Heterocyclic Compounds; D013141:Spiro Compounds; D012428:Ruthenium
keywords: asymmetric catalysis; dehydrative allylation; ketones; ruthenium; spiro compounds