Ring Transformations of Heterocyclic Compounds. XVIII [1]. Spiro[cyclohexadiene-indolines] with Three Stereocenters from Pyrylium Salts and Chiral Methyleneindolines - An Example of a High Diastereoselektive Ring Transformation

The diastereoselective synthesis of 6-aroyl-3,5-diarylspiro[cyclohexa-2,4-diene-1,2´-indolines] 4 possessing three stereocenters from 2,4,6-triaryl-pyrylium perchlorates 1 and chiral methyleneindolines 3, generated in situ by deprotonation of the corresponding 3H-indolium perchlorates 2, in the presence of triethylamine/acetic acid in ethanol by a 2,5-[C4+C2] pyrylium ring transformation is reported. Structure elucidation is performed by X-ray structure determinations of the spiro[cyclohexadiene-indolines] 4a, 4p and 4t. The influence of various substituents at C-3 of the methyleneindolines 3 on the stereochemistry of the transformation, mechanistic details as well as spectroscopic data of the products 4 are discussed.