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

2. Contents ・ Polycyclic Aromatic Hydrocarbons Introduction Conclusion Cyclization Reaction ・ Examples of Cyclization Reaction ・ Continuous Cyclization Reaction ・ Transannular Cyclization Reaction My Project

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

4. Examples of Cyclization Reaction Scheme 1. Diels-Alder reaction Scheme 2. Friedel-Crafts reaction Scheme 3. Oxidative and reductive reaction ~Cyclization reaction~ Zander, M. et al. J. Chem. Soc. 1957, 4616–4619. Bednya, N. P. et al. Zh. Obshch. Khim. 1937, 7, 2919–2924. Müllen, K. et al. Chem. Ber. 1991, 124, 2091–2100.

5. Bergman Cyclization Reaction Scheme 4. Bergman reaction Bergman, R. G. et al., J. Am. Chem. Soc. 1972. 94. 660. Colkins, T. L. Tetrahedron Lett. 1992, 33, 2315-2318. ~Cyclization reaction~

6. Tandem Cyclization Reaction by Electrophile and Radical Reagent Scheme 5. Cyclization by electrophilic and radical reagent ~Cyclization reaction~ Lutz, V. et al. Angew. Chem. Int. Ed. 2003, 42, 5757−5760. Ghiviriga, I. et al. J. Am. Chem. Soc. 2008, 130, 11535–11545. Tandem Cyclization ・・・連続環化

7. Transannular Cyclization Reaction of [10]annulene Scheme 6. Electrophilic reaction of dinaphtho[10]annulene Clar, E. et al. Chem. Ber. 1955, 88, 1520 Sondheimer, F. et al. J. Am. Chem. Soc., 1968, 90,530 – 531 ~Cyclization reaction~ Tobe. Y, Org. Lett. 2009, 11, 4104–4106. Scheme 7. Two synthetic methods of Zethrene Transannular cyclization ・・・渡環環化

8. Transannular Cyclization Reaction of [14]annulene Scheme 8. Nucleophilic reaction of dehydrotribenzo[14]annulene ~Cyclization reaction~ butadiyne

9. My Project Scheme 9. Transannular cyclization reaction of tetrabenzo[14]annulene butadiyne

10. Conclusion ・ Recently, PAHs are expected to be the functionalized organic materials. ・ Transannular cyclization reaction is considered of value for synthetic method to novel PAHs. ・ Tetrabenzo[14]annulene that is target compound has been synthesized.