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We present a six-step cascade that converts 1,3-distyrylbenzenes (bis-stilbenes) into nonsymmetric pyrenes in 40–60% yields. This sequence merges photochemical steps, E,Z-alkene isomerization, a 6π photochemical electrocyclization (Mallory photocyclization); the new bay region cyclization, with two radical iodine-mediated aromatization steps; and an optional aryl migration. This work illustrates how the inherent challenges of engineering excited state reactivity can be addressed by logical design. An unusual aspect of this cascade is that the same photochemical process (the Mallory reaction) is first promoted and then blocked in different stages within a photochemical cascade. The use of blocking groups is the key feature that makes simple bis-stilbenes suitable substrates for directed double cyclization. While the first stilbene subunit undergoes a classic Mallory photocyclization to form a phenanthrene intermediate, the next ring-forming step is diverted from the conventional Mallory path into a photocyclization of the remaining alkene at the phenanthrene’s bay region. Although earlier literature suggested that this reaction is unfavorable, we achieved this diversion via incorporation of blocking groups to prevent the Mallory photocyclization. The two photocyclizations are assisted by the relief of the excited state antiaromaticity. Reaction selectivity is controlled by substituent effects and the interplay between photochemical and radical reactivity. Furthermore, the introduction of donor substituents at the pendant styrene group can further extend this photochemical cascade through a radical 1,2-aryl migration. Rich photophysical and supramolecular properties of the newly substituted pyrenes illustrate the role of systematic variations in the structure of this classic chromophore for excited state engineering.
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Localized Antiaromaticity Hotspot Drives Reductive Dehydrogenative Cyclizations in Bis- and Mono-Helicenes
We describe reductive dehydrogenative cyclizations that form hepta-, nona-, and decacyclic anionic graphene subunits from mono- and bis-helicenes with an embedded five-membered ring. The reaction of bis-helicenes can either proceed to the full double annulation or be interrupted by addition of molecular oxygen at an intermediate stage. The regioselectivity of the interrupted cyclization cascade for bis-helicenes confirms that relief of antiaromaticity is a dominant force for these facile ring closures. Computational analysis reveals the unique role of the preexisting negatively charged cyclopentadienyl moiety in directing the second negative charge at a specific remote location and, thus, creating a localized antiaromatic region. This region is the hotspot that promotes the initial cyclization. Computational studies, including MO analysis, molecular electrostatic potential maps, and NICS(1.7)ZZ calculations, evaluate the interplay of the various effects including charge delocalization, helicene strain release, and antiaromaticity. The role of antiaromaticity relief is further supported by efficient reductive closure of the less strained monohelicenes where the relief of antiaromaticity promotes the cyclization even when the strain is substantially reduced. The latter finding significantly expands the scope of this reductive alternative to the Scholl ring closure.
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- PAR ID:
- 10335316
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- ISSN:
- 0002-7863
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/jacs.2c03681
