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
Externally publishedYes

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Regioselectivity
Biomolecules
Binding sites
Bovine Serum Albumin
Complexation
Stoichiometry
Dimers
Molecules
Substrates
Buffers
Binding Sites
2-anthracenecarboxylate

ASJC Scopus subject areas

  • Chemistry(all)

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Bovine serum albumin-mediated enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate. / Wada, Takehiko; Nishijima, Masaki; Fujisawa, Tai; Sugahara, Norimitsu; Mori, Tadashi; Nakamura, Asao; Inoue, Yoshihisa.

In: Journal of the American Chemical Society, Vol. 125, No. 25, 25.06.2003, p. 7492-7493.

Research output: Contribution to journalArticle

Wada, Takehiko ; Nishijima, Masaki ; Fujisawa, Tai ; Sugahara, Norimitsu ; Mori, Tadashi ; Nakamura, Asao ; Inoue, Yoshihisa. / Bovine serum albumin-mediated enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate. In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 25. pp. 7492-7493.
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