Highly diastereoselective synthesis of polycyclic amines via redox neutral C-H functionalizationElectronic supplementary information (ESI) available. CCDC 1054103 (3c), 1401266 (3p) and 1054104 (4c). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5nj01706h

Synthesis of polycyclic amines was achieved by benzoic acid catalysed reaction of 1-aryl THIQs and 1-aryl trypolines with o -allyl salicylaldehydes through the in situ generated azomethine ylide intermediates that undergo intramolecular [3+2]-cycloadditions with four new stereogenic centers in excellent diastereoselectivities under simple and mild conditions. Construction of polycyclic amines via C-H functionalization and 3+2 cycloaddition with high diastereoselectivities was achieved under mild conditions.