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Site-Selective [2+2+n] Cycloadditions for Rapid, Scalable Access to Alkynylated Polycyclic Aromatic Hydrocarbons

preprint
submitted on 03.12.2019 and posted on 11.12.2019 by Gavin R. Kiel, Harrison Bergman, T. Don Tilley
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 Mo catalysis to afford large, PAH-containing arylene ethylene macrocycles, which possess a range of cavity sizes reaching well into the nanometer regime. More generally, this work is a demonstration of how site-selective reactions can be harnessed to rapidly build up structural complexity in a practical, scalable fashion.

Funding

National Science Foundation, Grant No. CHE-1708210

History

Email Address of Submitting Author

gkiel3@MIT.edu

Institution

University of California, Berkeley

Country

United States

ORCID For Submitting Author

0000-0001-6449-8547

Declaration of Conflict of Interest

None

Exports