Liu Yidong, Wu Xiaoyan, Li Shan, Xue Lu, Shan Chunhui, Zhao Zhengxing, Yan Hailong
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing, 401331, P. R. China.
Angew Chem Int Ed Engl. 2018 May 28;57(22):6491-6495. doi: 10.1002/anie.201801824. Epub 2018 May 3.
The enantioselective construction of axially chiral aryl-naphthopyran skeletons was realized by organocatalytic atroposelective intramolecular [4+2] cycloaddition of in situ generated vinylidene ortho-quinone methides, from 2-ethynylphenol derivatives, with alkynes. Through this method, the heteroatropisomers were obtained with excellent yields and enantioselectivities. Moreover, a speculative model of the stereochemical outcome is proposed based on preliminary mechanistic studies. The products having various functional groups can be easily transformed into valuable intermediates as either potential ligands or organocatalysts.
通过有机催化原位生成的亚乙烯基邻醌甲基化物（由2-乙炔基苯酚衍生物生成）与炔烃的分子内[4+2]环加成反应，实现了轴向手性芳基萘并吡喃骨架的对映选择性构建。通过这种方法，以优异的产率和对映选择性获得了杂轴手性异构体。此外，基于初步的机理研究提出了立体化学结果的推测模型。具有各种官能团的产物可以很容易地转化为有价值的中间体，作为潜在的配体或有机催化剂。
