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. 2021 Dec 9;27(69):17322-17325.
doi: 10.1002/chem.202103098. Epub 2021 Nov 10.

Domino Dehydrative π-Extension: A Facile Path to Extended Perylenes and Terrylenes

Mikhail Feofanov  1   2 , Vladimir Akhmetov  2 , Konstantin Amsharov  1   2
Affiliations

Domino Dehydrative π-Extension: A Facile Path to Extended Perylenes and Terrylenes

Mikhail Feofanov et al. Chemistry. .

Abstract

Herein, we report a new method for synthesis of extended perylenes and terrylenes. The technique is based on the cascade dehydrative π-extensions (DPEX) of aryl aldehydes, in which stepwise annulations activate previously "dormant" substituents. Two- and fourfold cyclizations of 3-aryl-biphenyl-2,2'-dicarbaldehydes offer a rapid path to unsymmetrical perylenes and elusive terrylene derivatives, respectively. DPEX of 3,3''-(phenanthrene-1,8-diyl)bis (([1,1'-biphenyl]-2,2'-dicarbaldehyde)) leads to the biradical structure, which proceeds in situ into oxidative electrocyclization at room temperature. The described domino process complements and expands DPEX approach to a large family of fused acenes and related PAHs.

Keywords: domino reactions; perylenes; pi-extension; polycyclic aromatic compounds; terrylenes.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Reported synthesis of terrylene (top) and the synthesis of tribenzo terrylene NG1 (bottom) demonstrating the efficiency of the domino DPEX approach.
Scheme 2
Scheme 2
a) Synthesis of fused acene demonstrating tolerance towards “misplaced” formyl groups under DPEX conditions. b) Description of Domino DPEX.
Scheme 3
Scheme 3
Synthesis of extended perylene and terrylenes by a) twofold, and b) fourfold cyclisation. c) Synthesis of NG6 in a fivefold domino‐DPEX accompanied by spontaneous electrocyclization. Conditions of domino‐DPEX: SnCl2, iPrOH, H2SO4, CH2Cl2.
Scheme 4
Scheme 4
Comparison of two‐ and fourfold Domino‐DPEX explaining the low yield in the case of twofold cyclisation as a result of the formation of highly reactive intermediates.
Figure 1
Figure 1
UV/vis spectra of NG1‐NG5. The spectra were recorded in CH2Cl2.
See this image and copyright information in PMC

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