We recently reported that β-hydroxy-α-diazo ketones react with Lewis acids to give fused bicyclic cyclopentenone products. This reaction occurs through the formation of a destabilized linear vinyl cation (2) that rearranges via a 1,2-shift to provide a more stable cyclic vinyl cation (3), which then inserts into an unactivated C-H bond to provide the cyclopentenone product (4). We have since expanded our studies to include unsymmetric systems (1, R1≠R2), and in this presentation we report our results detailing the migratory aptitude of different groups in the 1,2-shift event (i.e. 2 → 3). We have also been exploring the use of the vinyl cation intermediates in intramolecular reactions other than C-H insertion. For example, we recently reported that the vinyl cation intermediates could be captured by pendent aromatic rings to give tricyclic 1-indenone products. We have since expanded these studies to include alkenes as the nucleophilic capturing agent, and our results from these studies will be reported as well.

Vinyl cations as cyclopentenone precursors via C–H insertion and alkene addition reactions

2019 Fall National Meeting

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