Mコロ-芦田研究室.pptVIP

Tobe Laboratory M1 Yamane Hiroshi Synthesis of novel polycyclic aromatic hydrocarbons by transannular cyclization of dehydrobenzoannulenes Polycyclic Aromatic Hydrocarbons (PAH) PAH???多環状芳香族化合物 picene 9,9’-bifluorenylidene Superconducting materials K - Doped 20K Electron Acceptors of Lightweight Organic devices Kubozono, Y. et al. Nature, 2010, 464, 76-79. Wudl, F. et al. Angew. Chem. Int. Ed. 2009, 49, 532-536. ~Introduction~ Reactivity of alkyne πbond σbond πbond Bond energy : σbond πbond(1) πbond(2) (kJ/mol) 369 268 202 Alkyne has high reactivity ~Introduction~ Tandem Cyclization Reaction by Electrophile Scheme 1. Tandem cyclization reaction by electrophilic Lutz, V. et al. Angew. Chem. Int. Ed. 2003, 42, 5757?5760. Tandem Cyclization???連続環化 * Low selectivity and low yield ~Introduction~ Motivation ?Low selectivity ?Low yield Noncyclic compounds Distance between acetylenes is loose Cyclic compounds Distance between acetylenes is fixed ?Improvement of selectivity ?Improvement of yield ?Induction of spontaneous reaction ~Purpose of my reserch~ Transannular cyclization for cyclic compounds Scheme 2. Transannular cyclization of cyclic compounds by several ways ~Purpose of my reserch~ Three-dimentional model of 1 Figure 1. Cariculated three-dimentional model of 1 (calculations are based on B3LYP/6-31G*) Prediction of reaction of 1 with nucleophile Scheme 3. Predicted cyclization reaction of 1 Synthesis route of 1 Sceme 4. Synthesis route of 1 Prediction of reaction of 7 Scheme 5. Reaction of 7 passed through benzyne intermediate Computational results for [2+4] diyne-yne cycloaddition ＋ 0.0 kcal/mol -51.4 E TS1 +36.5 High potential Energy reactive coordinate Aida A. et al. J. Org. Chem. 2011, 76, 9320-9328. Property of benzyne benzene benzyne Overlap of each p orbital is little sp2 orbitals are conjugated Electrons are localized Scheme 6. Diels-Alder reaction of benzyne and furan More destabilization stabilization Future work Sch