Site-selective [2 + 2 + n] cycloadditions for rapid, scalable access to alkynylated polycyclic aromatic hydrocarbons.

Chemical Science
Gavin R. KielT. Don Tilley

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are attractive synthetic building blocks for more complex conjugated nanocarbons, but their use for this purpose requires appreciable quantities of a PAH with reactive functional groups. Despite tremendous recent advances, most synthetic methods cannot satisfy these demands. Here we present a general and scalable [2 + 2 + n] (n = 1 or 2) cycloaddition strategy to access PAHs that are decorated with synthetically versatile alkynyl groups and its application to seven structurally diverse PAH ring systems (thirteen new alkynylated PAHs in total). The critical discovery is the site-selectivity of an Ir-catalyzed [2 + 2 + 2] cycloaddition, which preferentially cyclizes tethered diyne units with preservation of other (peripheral) alkynyl groups. The potential for generalization of the site-selectivity to other [2 + 2 + n] reactions is demonstrated by identification of a Cp2Zr-mediated [2 + 2 + 1]/metallacycle transfer sequence for synthesis of an alkynylated, selenophene-annulated PAH. The new PAHs are excellent synthons for macrocyclic conjugated nanocarbons. As a proof of concept, four were subjected to alkyne metathesis catalysis to afford large, PAH-containing arylene ethylene macrocycles, ...Continue Reading

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Citations

Aug 22, 2020·Angewandte Chemie·Alois FürstnerChristophe Copéret
Jun 5, 2021·Journal of the American Chemical Society·Harrison M BergmanT Don Tilley
Aug 6, 2021·Chemical Science·Shaofeng HuangWei Zhang
May 27, 2020·Journal of the American Chemical Society·Gavin R KielT Don Tilley
Sep 15, 2021·Journal of the American Chemical Society·Alois Fürstner
Oct 5, 2021·Chemical Communications : Chem Comm·Xin ZhouSemin Lee

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