Cycloaddition Initiated by Ynolates: High-Energy Dianion Equivalents as a Molecular Glue

In this paper, ynolate-initiated cycloaddition (annulation) to form a range of carbocycles and heterocycles is described. Ynolates consist of a ketene anion equivalent, which contains both nucleophilic and electrophilic moieties, and a carbodianion equivalent that achieves double addition. Hence, in addition to the usual [n+2] cycloaddition, ynolates can perform formal [n+1]-type annulations. Their high-energy performance has been demonstrated by their triple addition to arynes to generate triptycenes, in which the C-C triple bond of ynolates is cleaved. The synthetic applications of these methods, including natural products synthesis, are also described.

Automated summary

This paper describes the ynolate-initiated cycloaddition reaction to form a variety of carbocycles and heterocycles. Ynolates have the ability to achieve double addition and can perform formal [n+1]-type annulations, demonstrating their high-energy performance. The synthetic applications of these methods, including natural products synthesis, are discussed as well.