title: Synthesis of chiral 1-substituted tetrahydroisoquinolines by the intramolecular 1,3-chirality transfer reaction catalyzed by Bi(OTf)3.
abstract: The intramolecular 1,3-chirality transfer reaction of chiral amino alcohols 1 with 99% ee was developed to construct chiral 1-substituted tetrahydroisoquinoline 2. Bi(OTf)(3) (10 mol %)-catalyzed cyclization of 1 (R = H) afforded (S)-1-(E)-propenyl tetrahydroisoquinoline 2 (R = H) in 83% yield with a ratio of 98:2. The stereochemistry at the newly formed chiral center was produced by a syn S(N)2'-type process. In this reaction, the substituent on the benzene ring of 1 significantly affected the reactivities and selectivities. A plausible reaction mechanism was proposed.
authors.affiliation: Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8412, Japan. kawai@mb.kyoto-phu.ac.jp
authors.forename: Nobuyuki
authors.initials: N
authors.lastname: Kawai
authors.forename: Ryuzou
authors.initials: R
authors.lastname: Abe
authors.forename: Mika
authors.initials: M
authors.lastname: Matsuda
authors.forename: Jun'ichi
authors.initials: J
authors.lastname: Uenishi
mesh_terms: D002384:Catalysis; D003500:Cyclization; D008698:Mesylates / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium; D013237:Stereoisomerism; D044005:Tetrahydroisoquinolines / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D008698:Mesylates; D044005:Tetrahydroisoquinolines; C445789:Bi(OTf)3; D010165:Palladium