Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne peri-Annulations: Radical Cascades Converging on the Same Aromatic Core

Edgar Gonzalez-Rodriguez, Miguel A. Abdo, Gabriel Dos Passos Gomes, Suliman Ayad, Frankie D. White, Nikolay P. Tsvetkov, Kenneth Hanson, Igor V. Alabugin

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

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.

Original languageEnglish
Pages (from-to)8352-8366
Number of pages15
JournalJournal of the American Chemical Society
Volume142
Issue number18
DOIs
StatePublished - May 6 2020
Externally publishedYes

Funding

E.G.-R. is thankful for the support provided by CONACYT throughout his graduate studies. Financial support of this work by the National Science Foundation is gratefully acknowledged (CHE-1800329). Computational resources were provided by NSF XSEDE (TG-CHE160006) and FSU Research Computing Center. G.P.G. thanks Professor Alan Aspuru-Guzik (University of Toronto) for the support. E.G.-R. is thankful for the support provided by CONACYT throughout his graduate studies. Financial support of this work by the National Science Foundation is gratefully acknowledged (CHE-1800329). Computational resources were provided by NSF XSEDE (TG-CHE160006) and FSU Research Computing Center. G.P.G. thanks Professor Alán Aspuru-Guzik (University of Toronto) for the support.

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