Regioselective Molecularly Imprinted Reaction Field for [4 + 4] Photocyclodimerization of 2-Anthracenecarboxylic Acid.
Molecularly imprinted cavities have functioned as a regioselective reaction field for the [4 + 4] photocyclodimerization of 2-anthracenecarboxylic acid (2-AC). Molecularly imprinted polymers were prepared by precipitation polymerization of N-methacryloyl-4-aminobenzamidine as a functional monomer to form a complex with template 2-AC and ethylene glycol dimethacrylate as a crosslinking monomer. The 2-AC-imprinted cavities thus constructed preferentially bound 2-AC with an affinity greater than that toward structurally related 9-anthracenecarboxylic acid, 2-aminoanthracene, and unsubstituted anthracene. Moreover, from the four possible regioisomeric cyclodimers, they mediated the [4 + 4] photocyclodimerization of 2-AC specifically to the anti-head-to-tail (anti-HT) isomer. This indicates that the imprinted cavities accommodate two 2-AC molecules in an anti-HT manner, thereby facilitating the subsequent regioselective photocyclodimerization.
Graduate School of Engineering, Kobe University , 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
Satoshi
S
Nakai
Graduate School of Engineering, Kobe University , 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
Hirobumi
H
Sunayama
Graduate School of Engineering, Kobe University , 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
Yukiya
Y
Kitayama
Masaki
M
Nishijima
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University , 2-1-1, Katahira, Aoba-ku, Sendai 980-8577, Japan.
Takehiko
T
Wada
Yoshihisa
Y
Inoue
Graduate School of Engineering, Kobe University , 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
Toshifumi
0000-0002-5641-2333
T
Takeuchi