Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5/A8, 625 00 Brno, Czech Republic.
Org Lett. 2011 Dec 16;13(24):6556-9. doi: 10.1021/ol202892r. Epub 2011 Nov 17.
An electronic excited-state switching strategy has been utilized to control the selectivity of a key photochemical step in the total synthesis of indanorine. The excited-state character of 4,5-dimethoxy-2-methylphenacyl epoxide was changed from an unfavorable (3)π,π* state to a productive (3)n,π* state by a temporary structural modification, resulting in a relatively efficient and high-yielding formation of an indanone derivative. The corresponding structural modification was selected on the basis of quantum chemical calculations prior to the synthesis.
利用电子激发态转换策略来控制 indanorine 全合成中关键光化学反应步骤的选择性。通过临时的结构修饰，将 4,5-二甲氧基-2-甲基苯乙酮环氧化物的激发态特性从不利的 (3)π,π* 态转变为有利的 (3)n,π* 态，从而相对高效高产地形成了一种茚满酮衍生物。在合成之前，根据量子化学计算选择了相应的结构修饰。
