Pressure and temperature-controlled enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate mediated by secondary face- and skeleton-modified γ-cyclodextrins

Cheng Yang, Asao Nakamura, Gaku Fukuhara, Yumi Origane, Tadashi Mori, Takehiko Wada, Yoshihisa Inoue

Research output: Contribution to journalArticle

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Abstract

A series of secondary-face-substituted and skeleton-modified γ-cyclodextrins (γ-CDs) were prepared as chiral hosts for enantiodifferentiating [4+4] photocyclodimerization reactions of 2-anthracenecarboxylic acid (AC). These γ-CD derivatives form stable ternary complexes with ACs, with altroside-bearing γ-CDs undergoing induced-fit conformational changes upon complexation, and the photocyclodimerization of AC was, thus, dramatically accelerated. The enantiomeric excess (ee) of anti-head-to-head cyclodimer 3 was greatly enhanced in general with altroside-bearing γ-CDs 7-9. Although mono-altro-γ- CD 9 and 3A-azido-3A-deoxy-altro-γ-CD 7 gave 2 in ee's smaller than those obtained with native γ-CD, 3A-amino- 3A-deoxy-altro-γ-CD 8 yielded 2 in much higher ee's, which is likely to be ascribed to the combined effects of the less-symmetric cavity and the electrostatic interactions. The influence of temperature and high pressure on the supramolecular photochirogenic reaction has been investigated in depth. An ee as high as 71% was obtained for cyclodimer 2 in the photocyclodimerization of AC mediated by 8 at 210 MPa and -21.5 °C.

Original languageEnglish
Pages (from-to)3126-3136
Number of pages11
JournalJournal of Organic Chemistry
Volume71
Issue number8
DOIs
Publication statusPublished - 2006 Apr 14
Externally publishedYes

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Bearings (structural)
Cyclodextrins
Acids
Coulomb interactions
Complexation
Derivatives
Temperature
2-anthracenecarboxylate

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Pressure and temperature-controlled enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate mediated by secondary face- and skeleton-modified γ-cyclodextrins. / Yang, Cheng; Nakamura, Asao; Fukuhara, Gaku; Origane, Yumi; Mori, Tadashi; Wada, Takehiko; Inoue, Yoshihisa.

In: Journal of Organic Chemistry, Vol. 71, No. 8, 14.04.2006, p. 3126-3136.

Research output: Contribution to journalArticle

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abstract = "A series of secondary-face-substituted and skeleton-modified γ-cyclodextrins (γ-CDs) were prepared as chiral hosts for enantiodifferentiating [4+4] photocyclodimerization reactions of 2-anthracenecarboxylic acid (AC). These γ-CD derivatives form stable ternary complexes with ACs, with altroside-bearing γ-CDs undergoing induced-fit conformational changes upon complexation, and the photocyclodimerization of AC was, thus, dramatically accelerated. The enantiomeric excess (ee) of anti-head-to-head cyclodimer 3 was greatly enhanced in general with altroside-bearing γ-CDs 7-9. Although mono-altro-γ- CD 9 and 3A-azido-3A-deoxy-altro-γ-CD 7 gave 2 in ee's smaller than those obtained with native γ-CD, 3A-amino- 3A-deoxy-altro-γ-CD 8 yielded 2 in much higher ee's, which is likely to be ascribed to the combined effects of the less-symmetric cavity and the electrostatic interactions. The influence of temperature and high pressure on the supramolecular photochirogenic reaction has been investigated in depth. An ee as high as 71{\%} was obtained for cyclodimer 2 in the photocyclodimerization of AC mediated by 8 at 210 MPa and -21.5 °C.",
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AU - Yang, Cheng

AU - Nakamura, Asao

AU - Fukuhara, Gaku

AU - Origane, Yumi

AU - Mori, Tadashi

AU - Wada, Takehiko

AU - Inoue, Yoshihisa

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AB - A series of secondary-face-substituted and skeleton-modified γ-cyclodextrins (γ-CDs) were prepared as chiral hosts for enantiodifferentiating [4+4] photocyclodimerization reactions of 2-anthracenecarboxylic acid (AC). These γ-CD derivatives form stable ternary complexes with ACs, with altroside-bearing γ-CDs undergoing induced-fit conformational changes upon complexation, and the photocyclodimerization of AC was, thus, dramatically accelerated. The enantiomeric excess (ee) of anti-head-to-head cyclodimer 3 was greatly enhanced in general with altroside-bearing γ-CDs 7-9. Although mono-altro-γ- CD 9 and 3A-azido-3A-deoxy-altro-γ-CD 7 gave 2 in ee's smaller than those obtained with native γ-CD, 3A-amino- 3A-deoxy-altro-γ-CD 8 yielded 2 in much higher ee's, which is likely to be ascribed to the combined effects of the less-symmetric cavity and the electrostatic interactions. The influence of temperature and high pressure on the supramolecular photochirogenic reaction has been investigated in depth. An ee as high as 71% was obtained for cyclodimer 2 in the photocyclodimerization of AC mediated by 8 at 210 MPa and -21.5 °C.

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