Ammonia-Driven Chirality Inversion and Enhancement in Enantiodifferentiating Photocyclodimerization of 2-Anthracenecarboxylate Mediated by Diguanidino-纬-cyclodextrin

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• 作者：Jiabin Yao ; Zhiqiang Yan ; Jiecheng Ji ; Wanhua Wu ; Cheng Yang ; Masaki Nishijima ; Gaku Fukuhara ; Tadashi Mori ; Yoshihisa Inoue
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：May 14, 2014
• 年：2014
• 卷：136
• 期：19
• 页码：6916-6919
• 全文大小：267K
• 年卷期：v.136,no.19(May 14, 2014)
• ISSN：1520-5126

文摘

In the supramolecular photocyclodimerization of 2-anthracenecarboxylate mediated by 6^A,6^D-diguanidino-纬-cyclodextrin (CD), the chiral sense and enantiomeric excess of the photoproduct were dynamic functions of temperature and cosolvent to afford the (M)-anti head-to-head cyclodimer in 64% ee in aqueous methanol at 鈭?0 掳C but the antipodal (P)-isomer in 86% ee in aqueous ammonia at 鈭?5 掳C, while the corresponding diamino-纬-CD host did not show such unusual photochirogenic behaviors. The ee landscape was very steep against the temperature and sign-inverted against the ammonia content to reveal the opposite temperature dependence at low and high ammonia contents, for which an altered solvent structure and/or guanidinium鈥揷arboxylate interaction mode would be responsible.