ArticleJournal of the American Chemical Society2020
Impact of Excited-State Antiaromaticity Relief in a Fundamental Benzene Photoreaction Leading to Substituted Bicyclo[3.1.0]hexenes.
Article in Journal of the American Chemical Society, 2020. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 17 papers.
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Who cites it
17 citing papers in PubMed, 61 citations in OpenAlex.
- Large Stokes shift fluorophores fromChemical science · 2026Article
- Excited-State Antiaromaticity in Nonbenzenoid Aromatics: Examining the Dynamics of Intramolecular Proton Transfer With a Small Driving Force.Angewandte Chemie (International ed. in English) · 2026Article
- Singlet machine learning photodynamics reveal competing inversion paths of methylated cyclooctatetrathiophene.Chemical science · 2026Article
- Switching Shapes: Reversible Three Species Photoisomerization of Substituted 1,2-Dihydro-1,2-azaborinines.Journal of the American Chemical Society · 2026Article
- Reactivity umpolung of the cycloheptatriene core in hexa(methoxycarbonyl)cycloheptatriene.Beilstein journal of organic chemistry · 2026Article
- Photocyclization of Alkenes and Arenes: Penetrating Through Aromatic Armor with the Help of Excited State Antiaromaticity.Chemistry (Basel, Switzerland) · 2025Article
- Regioisomeric Engineering for Multicharge and Spin Stabilization in Two-Electron Organic Catholytes.Journal of the American Chemical Society · 2025Article
- Aromaticity Reversal Induced by Vibrations in Cyclo[16]carbon.Journal of the American Chemical Society · 2023Article
- The application of aromaticity and antiaromaticity to reaction mechanisms.Fundamental research · 2023Review
- Photochemical Uncaging of Aldehydes and Ketones via Photocyclization/Fragmentation Cascades of Enyne Alcohols: An Unusual Application for a Cycloaromatization Process.Molecules (Basel, Switzerland) · 2023Article
- Reshaping aromatic frameworks: expansion of aromatic system drives metallabenzenoids to metallapentalenes.Chemical science · 2023Article
- Baird's rules at the tipping point.Nature chemistry · 2022Article
- Barrier-Lowering Effects of Baird Antiaromaticity in Photoinduced Proton-Coupled Electron Transfer (PCET) Reactions.Journal of the American Chemical Society · 2021Article
- Rethinking Uncaging: A New Antiaromatic Photocage Driven by a Gain of Resonance Energy.Chemistry (Weinheim an der Bergstrasse, Germany) · 2021Article
- Relief of excited-state antiaromaticity enables the smallest red emitter.Nature communications · 2021Article
- Antiaromaticity Gain Activates Tropone and Nonbenzenoid Aromatics as Normal-Electron-Demand Diels-Alder Dienes.Organic letters · 2020Article
- Electron-driven proton transfer relieves excited-state antiaromaticity in photoexcited DNA base pairs.Chemical science · 2020Article
Corrections and comments
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Authors and funding
15 authors at 3 institutions in 3 countries.
Funding
No grant is acknowledged in the PubMed record.
Abstract
Benzene exhibits a rich photochemistry which can provide access to complex molecular scaffolds that are difficult to access with reactions in the electronic ground state. While benzene is aromatic in its ground state, it is antiaromatic in its lowest ππ* excited states. Herein, we clarify to what extent relief of excited-state antiaromaticity (ESAA) triggers a fundamental benzene photoreaction: the photoinitiated nucleophilic addition of solvent to benzene in acidic media leading to substituted bicyclo[3.1.0]hex-2-enes. The reaction scope was probed experimentally, and it was found that silyl-substituted benzenes provide the most rapid access to bicyclo[3.1.0]hexene derivatives, formed as single isomers with three stereogenic centers in yields up to 75% in one step. Two major mechanism hypotheses, both involving ESAA relief, were explored through quantum chemical calculations and experiments. The first mechanism involves protonation of excited-state benzene and subsequent rearrangement to bicyclo[3.1.0]hexenium cation, trapped by a nucleophile, while the second involves photorearrangement of benzene to benzvalene followed by protonation and nucleophilic addition. Our studies reveal that the second mechanism is operative. We also clarify that similar ESAA relief leads to puckering of S
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