New York University Abu Dhabi , P.O. Box 129188, Abu Dhabi , United Arab Emirates.
Department of Chemistry , University of Georgia , Athens , Georgia 30602 , United States.
J Org Chem. 2019 Jun 7;84(11):7342-7353. doi: 10.1021/acs.joc.9b01031. Epub 2019 May 28.
The direct release of dialkylanilines was achieved by controlling the outcome of a photorearrangement reaction promoted by the (8-cyano-7-hydroxyquinolin-2-yl)methyl (CyHQ) photoremovable protecting group. The substrate scope was investigated to obtain structure-activity relationships and to propose a reaction mechanism. Introducing a methyl substituent at the 2-methyl position of the CyHQ core enabled the bypass of the photorearrangement and significantly improved the aniline release efficiency. We successfully applied the strategy to the photoactivation of mifepristone (RU-486), an antiprogestin drug that is also used to induce the LexPR gene expression system in zebrafish and the gene-switch regulatory system based on the pGL-VP chimeric regulator in mammals.
通过控制（8-氰基-7-羟基喹啉-2-基）甲氧基（CyHQ）光保护基团促进的光重排反应的结果，实现了二芳基胺的直接释放。研究了底物范围，以获得构效关系并提出反应机制。在 CyHQ 核的 2-甲基位置引入甲基取代基可绕过光重排并显著提高苯胺的释放效率。我们成功地将该策略应用于米非司酮（RU-486）的光激活，米非司酮是一种抗孕激素药物，也用于诱导斑马鱼中的 LexPR 基因表达系统和基于 pGL-VP 嵌合调节剂的基因开关调节系统。
