Supramolecular photochirogenesis. 2. Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by 6-O-modified cyclodextrins

Y. Inoue, T. Wada, N. Sugahara, K. Yamamoto, K. Kimura, L. H. Tong, X. M. Gao, Z. J. Hou, Y. Liu

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79 Citations (Scopus)

Abstract

Supramolecular enantiodifferentiating photoisomerization of (Z)-cyclooctene (1Z) to the chiral (E)isomer (1E) via inclusion and sensitization by modified α-, β-, and/or γ-cyclodextrin derivatives, possessing benzoate (2a, 3a, 4a), isomeric phthalates (3b-d), and tethered benzamide (3e) chromophores, has been investigated in aqueous methanol solutions at varying temperatures. The photostationary-state 1E/1Z ratios obtained upon sensitization with 2-4 in 1:1 water-methanol reached 0.4-0.8, which are higher than the value of ca. 0.25 reported for sensitizations by conventional alkyl benzoates in hydrocarbon solvents, although the ratio was reduced to 0.2-0.4 in water or methanol. The sensitizations of 1Z by α- and γ-cyclodextrin benzoates (2a, 4a) with size-mismatched cavities gave 1E of poor enantiomeric excesses (ee's) smaller than 3 and 5%, respectively. In contrast, β-cyclodextrin derivatives (3a-e) afforded much higher ee's of up to 24%, depending on the solvent composition. Thus, the modification of cyclodextrin with a sensitizing group successfully enhanced the product through the excited-state supramolecular interaction within the cavity. Interestingly, the product ee's obtained with benzoate 3a and methyl phthalate 3b are not a simple function of either temperature or solvent, but are nicely correlated with the host occupancy or the percentage of occupied host. This means that the entropy factor plays an insignificant role in this supramolecular photochirogenesis system, which is in sharp contrast to the decisive role of entropy in the conventional (nonsupramolecular) counterpart performed in homogeneous solutions, where an inversion of product chirality by temperature variation is reported to occur.

Original languageEnglish
Pages (from-to)8041-8050
Number of pages10
JournalJournal of Organic Chemistry
Volume65
Issue number23
DOIs
Publication statusPublished - 2000 Nov 17
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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