四置換オレフィンの単純合成を可能にする 明快で新しい選択的反応の開発研究 • Stereocontrolled Synthesis of Tetrasubstituted Olefin • Differentially Substituted Olefin Templates Strategy 1 Background; it all started with the finding in 2011. Mihara, S. 2 (1-Iodovinyl) arene Sato, A. H. Mihara, S. • Tetrahedron Lett. 2012, 53, 3585-3589. • 特願 2012-170680 3 Vinyl halides 参考図書 天然物合成で活躍した反応(有機合成化学協会編、化学同人) 4 Approach to tetra-substituted olefin • ‘Stereocontrolled Synthesis of Tetrasubstituted Olefins’ Flynn, A. B.; Ogilvie, W. Chem. Rev. 2007, 107, 4698-4745. • Pharmaceuticals, electronic materials, and molecular machines. • Carbometallation of alkynes, Manipulation of existing olefins, Carbonyl olefination, Olefin metathesis, and ynolates. “Only recently (as from 1996) has serious study been directed toward this synthetic challenge.” • All encounter serious limitations due to its congested, and eclipsing nature. • Differentially Substituted Olefin Templates; DSOT Strategy 5 当時M1の佐藤君(現・黒金化成) 「電子豊富な基質は収率が良いような気が」 a Unpublished data, satd. aq. NH4Cl was added instead of H2O. 6 (E)-1-Haloenamide (E)-α only 99% (2.62 g) Sato, A. H.; Ohashi, K.; Iwasawa, T. Tetrahedron Lett. 2013, 54, 1309-1311. 特願 2012-278613 Sato, A. H. 7 Ohashi, K. (E)-1-(1-Halovinyl)-1H-indoles Sato, A. H.; Ohashi, K.; Ito, K.; Iwasawa, T. Tetrahedron Lett. 2013, 54, 2878-2881. 特願 2013-33888(2013年2月出願) Sato, A. H. 8 Ohashi, K. 1-Haloethenamides Ohashi, K.; Ide, M.; Mihara, S.; Iwasawa, T. Tetrahedron Lett. 2014, 55, 632-635 Ohashi, K. 9 Ide, M. Diyne can permit ten products as 1,3-butadienes. 10 (1E, 3E)-1,4-Dihalobuta-1,3-diene Ohashi, K. Ide, M. Ide, M.; Ohashi, K. Mihara, S.; Iwasawa, T. Tetrahedron Lett. 2014, 55, 2130-2133. 11 1/16, A single isomer 12 Mechanistic aspects perfect syn- Successful Key: Nitrogen coordinate to Silicon ? 13 Approach to tetra-substituted olefin 14 (E)-1-Bromo-2-iodoenamide 95%, 1.74 g ■Ide, M.; Yauchi, Y.; Iwasawa, T. Eur. J. Org. Chem. 2014, in press. ■特願 2014-014060, (2014年1月29日 出願) 75% 60% Ide, M. 75% 15 Yauchi, Y. Outlook: approach to tetra-substituted olefin • Differentially Substituted Olefin Templates; DSOT Strategy 16 Acknowledgements Ohashi, K. Ide, M. Yauchi, Y. • 知的財産本部 弁理士 櫻井 雄三 先生 • REC コーディネータ 筒井 長徳 様 17
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