Bottom-up synthesis of optically active oligonaphthalenes: Three different pathways for controlling axial chirality

Kazunori Tsubaki, Hiroyuki Tanaka, Kazuto Takaishi, Masaya Miura, Hiroshi Morikawa, Takumi Furuta, Kiyoshi Tanaka, Kaoru Fuji, Takahiro Sasamori, Norihiro Tokitoh, Takeo Kawabata

Research output: Contribution to journalArticle

27 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)6579-6587
Number of pages9
JournalJournal of Organic Chemistry
Volume71
Issue number17
DOIs
Publication statusPublished - Aug 18 2006
Externally publishedYes

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Chirality
Crystallization
Amines
Nuclear magnetic resonance
Thermodynamics
Derivatives
X rays
Kinetics
cupric chloride
pyrene
LDS 751
naphthalene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Bottom-up synthesis of optically active oligonaphthalenes : Three different pathways for controlling axial chirality. / Tsubaki, Kazunori; Tanaka, Hiroyuki; Takaishi, Kazuto; Miura, Masaya; Morikawa, Hiroshi; Furuta, Takumi; Tanaka, Kiyoshi; Fuji, Kaoru; Sasamori, Takahiro; Tokitoh, Norihiro; Kawabata, Takeo.

In: Journal of Organic Chemistry, Vol. 71, No. 17, 18.08.2006, p. 6579-6587.

Research output: Contribution to journalArticle

Tsubaki, K, Tanaka, H, Takaishi, K, Miura, M, Morikawa, H, Furuta, T, Tanaka, K, Fuji, K, Sasamori, T, Tokitoh, N & Kawabata, T 2006, 'Bottom-up synthesis of optically active oligonaphthalenes: Three different pathways for controlling axial chirality', Journal of Organic Chemistry, vol. 71, no. 17, pp. 6579-6587. https://doi.org/10.1021/jo060974v
Tsubaki, Kazunori ; Tanaka, Hiroyuki ; Takaishi, Kazuto ; Miura, Masaya ; Morikawa, Hiroshi ; Furuta, Takumi ; Tanaka, Kiyoshi ; Fuji, Kaoru ; Sasamori, Takahiro ; Tokitoh, Norihiro ; Kawabata, Takeo. / Bottom-up synthesis of optically active oligonaphthalenes : Three different pathways for controlling axial chirality. In: Journal of Organic Chemistry. 2006 ; Vol. 71, No. 17. pp. 6579-6587.
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