Herein, for the first time, we report the asymmetric synthesis of an unexpected stereoisomer of spirohexahydroindole a trienamine-catalysed remote olefin / isomerisation/[4 + 2]-cycloaddition reaction. The reaction afforded a vast library of aesthetically pleasing spirooxindole hexahydroindole scaffolds with exceptional enantio- and diastereo-selectivities (up to 95% yield, 99% ee and >99 : 1 dr). In addition, we demonstrated the synthetic transformation of enantiomerically pure spirooxindole hexahydroindoles to synthesize alkyl homologated spirooxindole hexahydroindole and fluoro-pyranooctahydroindole moieties with four and seven contiguous stereocenters, respectively, in excellent yield and selectivities. We have also demonstrated the evidence for the proposed pathway through NMR investigations.
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