title: Bottom-up synthesis of optically active oligonaphthalenes: three different pathways for controlling axial chirality.
abstract: The oxidative homocoupling of optically active binaphthalenes 1a-d with a stoichiometric amount of CuCl2 and amines afforded quaternaphthalenes 2a-d in up to 93% de. The high diastereoselectivities were achieved through three different pathways (epimerization of the axis together with diastereoselective crystallization, thermodynamic, and kinetic control pathways). The type of side chains on the naphthalene influenced which pathway dominates. Three pathways were applicable to octinaphthalenes (8a-d) and hexadecanaphthalene 10a with 46-99% de. The absolute configuration of the newly formed axial bond was determined by (1) X-ray crystallographic analysis, (2) transformation to known compounds 15 and 16, (3) CD spectra of oligonaphthalenes with two pyrene rings as exciton parts, and (4) the shift values in 13C NMR spectra of 13C-enriched derivatives 29-31 toward chiral shift reagent Eu(+tfc)3.
authors.affiliation: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan. tsubaki@fos.kuicr.kyoto-u.ac.jp
authors.forename: Kazunori
authors.initials: K
authors.lastname: Tsubaki
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Tanaka
authors.forename: Kazuto
authors.initials: K
authors.lastname: Takaishi
authors.forename: Masaya
authors.initials: M
authors.lastname: Miura
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Morikawa
authors.forename: Takumi
authors.initials: T
authors.lastname: Furuta
authors.forename: Kiyoshi
authors.initials: K
authors.lastname: Tanaka
authors.forename: Kaoru
authors.initials: K
authors.lastname: Fuji
authors.forename: Takahiro
authors.initials: T
authors.lastname: Sasamori
authors.forename: Norihiro
authors.initials: N
authors.lastname: Tokitoh
authors.forename: Takeo
authors.initials: T
authors.lastname: Kawabata
mesh_terms: D013058:Mass Spectrometry; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D009281:Naphthalenes; C031721:naphthalene