Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne peri-Annulations: Radical Cascades Converging on the Same Aromatic Core
- 4 April 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (18), 8352-8366
- https://doi.org/10.1021/jacs.0c01856
Abstract
A versatile synthetic route to distannyl-substituted polyarenes was developed via double radical peri-annulations. The cyclization precursors were equipped with propargylic OMe traceless directing groups (TDGs) for regioselective Sn-radical attack at the triple bonds. The two peri-annulations converge at a variety of polycyclic cores to yield expanded difunctionalized polycyclic aromatic hydrocarbons (PAHs). This approach can be extended to triple peri-annulations, where annulations are coupled with a radical cascade that connects two preexisting aromatic cores via a formal C-H activation step. The installed Bu3Sn groups serve as chemical handles for further functionalization via direct cross-coupling, iodination, or protodestannylation, and increase solubility of the products in organic solvents. Photophysical studies reveal that the Bu3Sn-substituted PAHs are moderately fluorescent, and their protodestannylation results in an up to 10-fold fluorescence quantum yield enhancement. DFT calculations identified the most likely possible mechanism of this complex chemical transformation involving two independent peri-cyclizations at the central core.Funding Information
- Division of Chemistry (CHE-1800329)
- Consejo Nacional de Ciencia y Tecnolog?a
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