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Synthesis of Novel Polycyclic Aromatic Hydrocarbons via Transannular Cyclization for Enhanced Yield and Selectivity

This study explores the transannular cyclization of dehydrobenzoannulenes to generate novel polycyclic aromatic hydrocarbons with improved yield and selectivity. The research investigates the reactivity of alkynes and presents a tandem cyclization reaction using electrophiles. The purpose is to enhance the yield and selectivity of cyclic compounds by inducing spontaneous reactions. The study predicts the cyclization reactions of specific compounds and explores the computational results of diyne-yne cycloaddition. Additionally, it delves into the Diels-Alder reaction of benzyne and furan, with future work planned to trap benzyne intermediates. The synthesis route, reaction predictions, and computational analyses provided will contribute to advancing the understanding of polycyclic aromatic hydrocarbons.

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Synthesis of Novel Polycyclic Aromatic Hydrocarbons via Transannular Cyclization for Enhanced Yield and Selectivity

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  1. Synthesis of novel polycyclic aromatic hydrocarbons by transannular cyclization of dehydrobenzoannulenes Tobe Laboratory M1 Yamane Hiroshi

  2. ~Introduction~ Polycyclic Aromatic Hydrocarbons (PAH) PAH・・・多環状芳香族化合物 picene K - Doped 9,9’-bifluorenylidene 20K Electron Acceptors of Lightweight Organic devices Superconducting materials Wudl, F. et al. Angew. Chem. Int. Ed. 2009, 49, 532-536. Kubozono, Y. et al. Nature, 2010, 464, 76-79.

  3. ~Introduction~ Reactivity of alkyne πbond πbond σbond Bond energy : σbond > πbond(1) >πbond(2) (kJ/mol) 369 268 202 Alkyne has high reactivity

  4. Tandem Cyclization Reaction by Electrophile ~Introduction~ Tandem Cyclization・・・連続環化 Lutz, V. et al. Angew. Chem. Int. Ed.2003, 42, 5757−5760. Scheme 1. Tandem cyclization reaction by electrophilic Low selectivity and low yield 4

  5. Cyclic compounds Distance between acetylenes is fixed ~Purpose of my reserch~ Motivation Noncyclic compounds Distance between acetylenes is loose ・Low selectivity ・Low yield ・Improvement of selectivity ・Improvement of yield ・Induction of spontaneous reaction

  6. ~Purpose of my reserch~ Transannular cyclization for cyclic compounds Scheme 2. Transannular cyclization of cyclic compounds by several ways

  7. Three-dimentional model of 1 Figure 1. Cariculated three-dimentional model of 1 (calculations are based on B3LYP/6-31G*)

  8. Prediction of reaction of 1 with nucleophile Scheme 3. Predicted cyclization reaction of 1

  9. Synthesis route of 1 Sceme 4. Synthesis route of 1

  10. Prediction of reaction of7 Scheme 5. Reaction of 7 passed through benzyne intermediate

  11. Computational results for [2+4] diyne-yne cycloaddition TS1 +36.5 ＋ 0.0 kcal/mol High potential Energy E -51.4 • reactive coordinate Aida A. et al. J. Org. Chem. 2011, 76, 9320-9328.

  12. Property of benzyne Overlap of each p orbital is little Electrons are localized benzene benzyne sp2 orbitals are conjugated More destabilization stabilization Scheme 6. Diels-Alder reaction of benzyne and furan

  13. Future work Scheme 8. Trapping of benzyne intermediate by furan

  14. Conclusion • Acetylene-integrated 1 is designed. • After the synthesis of 1, 7 is considered generated via benzyne intermediates. • I will confirm the presence of a benzyne intermediate by furan.

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