title: Enantioselective Cyanosilylation of Ketones with Lithium(I) Dicyanotrimethylsilicate(IV) Catalyzed by a Chiral Lithium(I) Phosphoryl Phenoxide.
abstract: A highly enantioselective cyanosilylation of ketones was developed by using a chiral lithium(I) phosphoryl phenoxide aqua complex as an acid/base cooperative catalyst. The pentacoordinate silicate generated in situ from Me3SiCN/LiCN acts as an extremely reactive cyano reagent. Described is a 30 gram scale reaction and the synthesis of the key precursor to (+)-13-hydroxyisocyclocelabenzine.
authors.affiliation: Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan.
authors.forename: Manabu
authors.initials: M
authors.lastname: Hatano
authors.affiliation: Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan.
authors.forename: Katsuya
authors.initials: K
authors.lastname: Yamakawa
authors.affiliation: Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan.
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Kawai
authors.affiliation: Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Horibe
authors.affiliation: Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan. ishihara@cc.nagoya-u.ac.jp.|Japan Science and Technology Agency (JST), CREST, Furo-cho, Chikusa, Nagoya, 464-8603, Japan. ishihara@cc.nagoya-u.ac.jp.
authors.forename: Kazuaki
authors.initials: K
authors.lastname: Ishihara
keywords: asymmetric synthesis; homogeneous catalysis; ketones; lithium; silicates