Department of Chemistry, Center for Heterocyclic Compounds, University of Florida, Gainesville, FL 32611 (USA).
Angew Chem Int Ed Engl. 2015 Dec 7;54(50):15202-6. doi: 10.1002/anie.201507848. Epub 2015 Oct 30.
A highly enantioselective copper-catalyzed alkynylation of quinolinium salts is reported. The reaction employs StackPhos, a newly developed imidazole-based chiral biaryl P,N ligand, and copper bromide to effect a three-component reaction between a quinoline, a terminal alkyne, and ethyl chloroformate. Under the reaction conditions, the desired products are delivered in high yields with ee values of up to 98 %. The transformation tolerates a wide range of functional groups with respect to both the alkyne and the quinoline starting materials and the products are easily transformed into useful synthons. Efficient, enantioselective syntheses of the tetrahydroquinoline alkaloids (+)-galipinine, (+)-angustureine, and (-)-cuspareine are reported.
据报道，一种高对映选择性的铜催化的喹啉盐炔基化反应。该反应采用了一种新开发的基于咪唑的手性联芳基 P，N 配体 StackPhos，以及溴化亚铜，实现了喹啉、末端炔烃和氯甲酸乙酯之间的三组分反应。在反应条件下，所需产物以高达 98%的 ee 值以高产率得到。该转化对炔烃和喹啉起始原料的官能团具有广泛的耐受性，并且产物易于转化为有用的合成子。报道了四氢喹啉生物碱(+)-galipinine、(+)-angustureine 和(-)-cuspareine 的高效、对映选择性合成。
