Bovine serum albumin-mediated enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate

Takehiko Wada, Masaki Nishijima, Tai Fujisawa, Norimitsu Sugahara, Tadashi Mori, Asao Nakamura, Yoshihisa Inoue

Research output: Contribution to journalArticle

91 Citations (Scopus)

Abstract

Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxyalate (AC) was performed at 25 °C in aqueous buffer solution (pH 7) in the presence of bovine-serum albumin (BSA) to afford four [4 + 4] cyclodimers, i.e., anti- and syn-head-to-tail (HT) (1 and 2) and anti- and syn-head-to-head (HH) dimers (3 and 4), of which only 2 and 3 are chiral. We found that (1) BSA possesses four sets of binding sites for AC of different affinities, stoichiometries, and chiral environment for photoreaction, which bind 1, 3, 2, and 3 AC molecules with binding constants of 5.3 × 107, 1.3 × 105, 1.4 × 104, and 3.0 × 103 M-1, respectively, (2) the regioselectivity of photodimerization is switched from HT to HH by adding BSA (the HH/HT ratio varies from 0.28 to 4.3), (3) BSA-mediated photodimerization of AC affords optically active products 2 and 3 of up to 29% and 41% ee, respectively. It is emphasized that the selective excitation of bound substrate, utilizing the spectral shift upon complexation with BSA, is not a prerequisite for efficient photochirogenesis using biomolecules.

Original languageEnglish
Pages (from-to)7492-7493
Number of pages2
JournalJournal of the American Chemical Society
Volume125
Issue number25
DOIs
Publication statusPublished - 2003 Jun 25

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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