Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO, 80309, USA.
Department of Chemistry, University of Colorado Denver, Campus Box 194, Denver, CO, 80217, USA.
Angew Chem Int Ed Engl. 2017 Sep 25;56(40):12206-12209. doi: 10.1002/anie.201706694. Epub 2017 Aug 23.
Reported is the enantioselective synthesis of tetracyclic indolines using silver(I)/chiral phosphoric acid catalysis. A variety of alkyne-tethered indoles are suitable for this process. Mechanistic studies suggest that the in situ generated silver(I) chiral phosphate activates both the alkyne and the indole nucleophile in the initial cyclization step through an intermolecular hydrogen bond and the phosphate anion promotes proton transfer. In addition, further modifications of the cyclization products enabled stereochemistry-function studies of a series of bioactive indolines.
报道了银（I）/手性磷酸催化的四环吲哚啉的对映选择性合成。各种炔烃连接的吲哚都适合该过程。机理研究表明，原位生成的银（I）手性磷酸通过分子间氢键激活炔烃和吲哚亲核试剂，在初始环化步骤中，磷酸阴离子促进质子转移。此外，对环化产物的进一步修饰使一系列生物活性吲哚的立体化学-功能研究成为可能。
