title: Dynamic Kinetic Resolution Approach for the Asymmetric Synthesis of Tetrahydrobenzodiazepines Using Transfer Hydrogenation by Chiral Phosphoric Acid.
abstract: Asymmetric synthesis of tetrahydrobenzodiazepines was achieved by transfer hydrogenation of dihydrobenzodiazepines with benzothiazoline having a hydrogen-bonding donor substituent by means of a newly synthesized chiral phosphoric acid. This method was applicable to various racemic dihydrobenzodiazepines to give the corresponding products in good yields with excellent diastereoselectivities and enantioselectivities taking advantage of the dynamic kinetic resolution. Furthermore, the effect of bulky substituent at 3,3'-position on the catalyst and hydrogen-bonding donor substituent on benzothiazoline was fully elucidated by the theoretical study.
authors.affiliation: Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo, 171-8588, Japan.
authors.forename: Kosaku
authors.initials: K
authors.lastname: Horiguchi
authors.affiliation: Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo, 171-8501, Japan.
authors.forename: Eri
authors.initials: E
authors.lastname: Yamamoto
authors.affiliation: Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo, 171-8588, Japan.|Department of Chemistry, Keio University, Hiyoshi, Kohoku-ku, Yokohama, Kanagawa, 223-8522, Japan.
authors.forename: Kodai
authors.initials: K
authors.lastname: Saito
authors.affiliation: Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo, 171-8501, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Yamanaka
authors.affiliation: Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo, 171-8588, Japan. takahiko.akiyama@gakushuin.ac.jp.
authors.forename: Takahiko
authors.identifier: 0000-0003-4709-4107
authors.initials: T
authors.lastname: Akiyama
keywords: dynamic kinetic resolution; heterocycles; hydrogenation; organocatalysis; stereoselective synthesis