Bovine serum albumin-mediated enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate

被引:92
作者
Wada, T
Nishijima, M
Fujisawa, T
Sugahara, N
Mori, T
Nakamura, A
Inoue, Y
机构
[1] Osaka Univ, Dept Mol Chem, Suita, Osaka 5650871, Japan
[2] JST, ICORP Entropy Control, Toyonaka, Osaka 5650085, Japan
[3] JST, ERATO Photochirogenesis Projects, Toyonaka, Osaka 5650085, Japan
关键词
D O I
10.1021/ja034641g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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. Copyright © 2003 American Chemical Society.
引用
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页码:7492 / 7493
页数:2
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