Differentially Substituted Olefin

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
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Stereocontrolled Synthesis of Tetrasubstituted Olefin
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Differentially Substituted Olefin Templates Strategy
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Background;
it all started with the finding in 2011.
Mihara, S.
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(1-Iodovinyl) arene
Sato, A. H. Mihara, S.
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Tetrahedron Lett. 2012, 53, 3585-3589.
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特願 2012-170680
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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）
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Approach to tetra-substituted olefin
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‘Stereocontrolled Synthesis of Tetrasubstituted Olefins’ Flynn, A. B.; Ogilvie, W. Chem. Rev. 2007, 107, 4698-4745.
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Pharmaceuticals, electronic materials, and molecular machines.
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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.”
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All encounter serious limitations due to its congested, and eclipsing nature.
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Differentially Substituted Olefin Templates; DSOT Strategy
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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Unpublished data, satd.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.
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(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.
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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.
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Ohashi, K.
1-Haloethenamides
Ohashi, K.; Ide, M.; Mihara, S.; Iwasawa, T. Tetrahedron Lett. 2014, 55, 632-635
Ohashi, K.
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Ide, M.
Diyne can permit ten products as 1,3-butadienes.
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(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.
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1/16, A single isomer
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Mechanistic aspects
perfect syn-
Successful Key:
Nitrogen
coordinate
to Silicon ?
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Approach to tetra-substituted olefin
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(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%
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Yauchi, Y.
Outlook: approach to tetra-substituted olefin
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Differentially Substituted Olefin Templates; DSOT Strategy
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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
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