Enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate catalyzed by 6A,6X -diamino-6A,6X-dideoxy-γ-cyclodextrins

Manipulation of product chirality by electrostatic interaction, temperature and solvent in supramolecular photochirogenesis

Cheng Yang, Gaku Fukuhara, Asao Nakamura, Yumi Origane, Kahee Fujita, De Qi Yuan, Tadashi Mori, Takehiko Wada, Yoshihisa Inoue

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

6A,6X-Dideoxy-6A,6X -diamino-γ-cyclodextrins (X = B, C, D and E) 5a-d were synthesized as chiral hosts for catalyzing the enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylic acid (ACA). The electrostatic interaction between 5a-d and ACA efficiently affected the preorganization of two ACA molecules within the γ-CD cavity, and improved the yields of head-to-head cyclodimers. By lowering the reaction temperature or solvent polarity, the electrostatic interaction was further enhanced. The anti-to-syn ratio of the head-to-head isomers gradually increased by changing the host from 5a to 5d (with increasing distance between the two amino groups on the CD rim), demonstrating a good structure-function relationship in this supramolecular photoreaction system. The chiral sense and enantiomeric excess of the photoproducts obtained are significantly affected, and even inverted, by solvent composition and reaction temperature. This temperature- and solvent-controlled chirality switching behavior is proven to originate from the contribution of non-zero differential entropy (ΔΔS‡) in the enantiodifferentiating process. This finding is the first example of a chirality inversion driven by entropy-related factors, such as solvent and temperature, in a non-sensitized asymmetric photoreaction. The sign of ΔΔ S‡ was switched by the composition of solvent and exhibited an excellent compensatory relationship against the differential enthalpy (ΔΔH‡), revealing that the photoenantiodifferentiation is governed not only by enthalpy but also by entropy, and also that the enantiodifferentiation mechanism does not vary throughout the whole system, irrespective of the condition changes.

Original languageEnglish
Pages (from-to)375-383
Number of pages9
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume173
Issue number3 SPEC. ISS.
DOIs
Publication statusPublished - 2005 Jul 15
Externally publishedYes

Fingerprint

Chirality
Cyclodextrins
Coulomb interactions
chirality
manipulators
electrostatics
products
Entropy
entropy
acids
interactions
Acids
Enthalpy
Temperature
enthalpy
temperature
rims
Chemical analysis
Isomers
polarity

Keywords

  • Anthracenecarboxylic acid
  • Chirality inversion
  • Diamino-γ-cyclodextrin
  • Enantiodifferentiation
  • Enthalpy-entropy compensation
  • Photocyclodimerization

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

Enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate catalyzed by 6A,6X -diamino-6A,6X-dideoxy-γ-cyclodextrins : Manipulation of product chirality by electrostatic interaction, temperature and solvent in supramolecular photochirogenesis. / Yang, Cheng; Fukuhara, Gaku; Nakamura, Asao; Origane, Yumi; Fujita, Kahee; Yuan, De Qi; Mori, Tadashi; Wada, Takehiko; Inoue, Yoshihisa.

In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 173, No. 3 SPEC. ISS., 15.07.2005, p. 375-383.

Research output: Contribution to journalArticle

@article{01f3f1042d2c45e389301c16a9df0e97,
title = "Enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate catalyzed by 6A,6X -diamino-6A,6X-dideoxy-γ-cyclodextrins: Manipulation of product chirality by electrostatic interaction, temperature and solvent in supramolecular photochirogenesis",
abstract = "6A,6X-Dideoxy-6A,6X -diamino-γ-cyclodextrins (X = B, C, D and E) 5a-d were synthesized as chiral hosts for catalyzing the enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylic acid (ACA). The electrostatic interaction between 5a-d and ACA efficiently affected the preorganization of two ACA molecules within the γ-CD cavity, and improved the yields of head-to-head cyclodimers. By lowering the reaction temperature or solvent polarity, the electrostatic interaction was further enhanced. The anti-to-syn ratio of the head-to-head isomers gradually increased by changing the host from 5a to 5d (with increasing distance between the two amino groups on the CD rim), demonstrating a good structure-function relationship in this supramolecular photoreaction system. The chiral sense and enantiomeric excess of the photoproducts obtained are significantly affected, and even inverted, by solvent composition and reaction temperature. This temperature- and solvent-controlled chirality switching behavior is proven to originate from the contribution of non-zero differential entropy (ΔΔS‡) in the enantiodifferentiating process. This finding is the first example of a chirality inversion driven by entropy-related factors, such as solvent and temperature, in a non-sensitized asymmetric photoreaction. The sign of ΔΔ S‡ was switched by the composition of solvent and exhibited an excellent compensatory relationship against the differential enthalpy (ΔΔH‡), revealing that the photoenantiodifferentiation is governed not only by enthalpy but also by entropy, and also that the enantiodifferentiation mechanism does not vary throughout the whole system, irrespective of the condition changes.",
keywords = "Anthracenecarboxylic acid, Chirality inversion, Diamino-γ-cyclodextrin, Enantiodifferentiation, Enthalpy-entropy compensation, Photocyclodimerization",
author = "Cheng Yang and Gaku Fukuhara and Asao Nakamura and Yumi Origane and Kahee Fujita and Yuan, {De Qi} and Tadashi Mori and Takehiko Wada and Yoshihisa Inoue",
year = "2005",
month = "7",
day = "15",
doi = "10.1016/j.jphotochem.2005.04.017",
language = "English",
volume = "173",
pages = "375--383",
journal = "Journal of Photochemistry and Photobiology A: Chemistry",
issn = "1010-6030",
publisher = "Elsevier",
number = "3 SPEC. ISS.",

}

TY - JOUR

T1 - Enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate catalyzed by 6A,6X -diamino-6A,6X-dideoxy-γ-cyclodextrins

T2 - Manipulation of product chirality by electrostatic interaction, temperature and solvent in supramolecular photochirogenesis

AU - Yang, Cheng

AU - Fukuhara, Gaku

AU - Nakamura, Asao

AU - Origane, Yumi

AU - Fujita, Kahee

AU - Yuan, De Qi

AU - Mori, Tadashi

AU - Wada, Takehiko

AU - Inoue, Yoshihisa

PY - 2005/7/15

Y1 - 2005/7/15

N2 - 6A,6X-Dideoxy-6A,6X -diamino-γ-cyclodextrins (X = B, C, D and E) 5a-d were synthesized as chiral hosts for catalyzing the enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylic acid (ACA). The electrostatic interaction between 5a-d and ACA efficiently affected the preorganization of two ACA molecules within the γ-CD cavity, and improved the yields of head-to-head cyclodimers. By lowering the reaction temperature or solvent polarity, the electrostatic interaction was further enhanced. The anti-to-syn ratio of the head-to-head isomers gradually increased by changing the host from 5a to 5d (with increasing distance between the two amino groups on the CD rim), demonstrating a good structure-function relationship in this supramolecular photoreaction system. The chiral sense and enantiomeric excess of the photoproducts obtained are significantly affected, and even inverted, by solvent composition and reaction temperature. This temperature- and solvent-controlled chirality switching behavior is proven to originate from the contribution of non-zero differential entropy (ΔΔS‡) in the enantiodifferentiating process. This finding is the first example of a chirality inversion driven by entropy-related factors, such as solvent and temperature, in a non-sensitized asymmetric photoreaction. The sign of ΔΔ S‡ was switched by the composition of solvent and exhibited an excellent compensatory relationship against the differential enthalpy (ΔΔH‡), revealing that the photoenantiodifferentiation is governed not only by enthalpy but also by entropy, and also that the enantiodifferentiation mechanism does not vary throughout the whole system, irrespective of the condition changes.

AB - 6A,6X-Dideoxy-6A,6X -diamino-γ-cyclodextrins (X = B, C, D and E) 5a-d were synthesized as chiral hosts for catalyzing the enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylic acid (ACA). The electrostatic interaction between 5a-d and ACA efficiently affected the preorganization of two ACA molecules within the γ-CD cavity, and improved the yields of head-to-head cyclodimers. By lowering the reaction temperature or solvent polarity, the electrostatic interaction was further enhanced. The anti-to-syn ratio of the head-to-head isomers gradually increased by changing the host from 5a to 5d (with increasing distance between the two amino groups on the CD rim), demonstrating a good structure-function relationship in this supramolecular photoreaction system. The chiral sense and enantiomeric excess of the photoproducts obtained are significantly affected, and even inverted, by solvent composition and reaction temperature. This temperature- and solvent-controlled chirality switching behavior is proven to originate from the contribution of non-zero differential entropy (ΔΔS‡) in the enantiodifferentiating process. This finding is the first example of a chirality inversion driven by entropy-related factors, such as solvent and temperature, in a non-sensitized asymmetric photoreaction. The sign of ΔΔ S‡ was switched by the composition of solvent and exhibited an excellent compensatory relationship against the differential enthalpy (ΔΔH‡), revealing that the photoenantiodifferentiation is governed not only by enthalpy but also by entropy, and also that the enantiodifferentiation mechanism does not vary throughout the whole system, irrespective of the condition changes.

KW - Anthracenecarboxylic acid

KW - Chirality inversion

KW - Diamino-γ-cyclodextrin

KW - Enantiodifferentiation

KW - Enthalpy-entropy compensation

KW - Photocyclodimerization

UR - http://www.scopus.com/inward/record.url?scp=21644487643&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=21644487643&partnerID=8YFLogxK

U2 - 10.1016/j.jphotochem.2005.04.017

DO - 10.1016/j.jphotochem.2005.04.017

M3 - Article

VL - 173

SP - 375

EP - 383

JO - Journal of Photochemistry and Photobiology A: Chemistry

JF - Journal of Photochemistry and Photobiology A: Chemistry

SN - 1010-6030

IS - 3 SPEC. ISS.

ER -