Enantioselective Synthesis of Epoxides Having a Tetrasubstituted Trifluoromethylated Carbon Center: Methylhydrazine-Induced Aerobic Epoxidation of β,β-Disubstituted Enones†
Hiroyuki Kawai
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorSatoshi Okusu
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorZhe Yuan
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorEtsuko Tokunaga
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorAkihito Yamano
Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima Tokyo 196-8666 (Japan)
Search for more papers by this authorDr. Motoo Shiro
Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima Tokyo 196-8666 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Norio Shibata
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)===Search for more papers by this authorHiroyuki Kawai
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorSatoshi Okusu
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorZhe Yuan
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorEtsuko Tokunaga
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorAkihito Yamano
Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima Tokyo 196-8666 (Japan)
Search for more papers by this authorDr. Motoo Shiro
Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima Tokyo 196-8666 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Norio Shibata
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)===Search for more papers by this authorThis study was financially supported in part by Grants-in-Aid for Scientific Research from the MEXT (Ministry of Education, Culture, Sports, Science and Technology) (24105513, Project No. 2304: Advanced Molecular Transformation by Organocatalysts). We thank the Asahi Glass Foundation for partial support. E.T. acknowledges Grants-in-Aid for Scientific Research for financial support (24915016). We also thank INSA de Rouen, France for providing an internship for Z.Y.
Graphical Abstract
Aus der Luft gegriffen: Die neuartige Titelreaktion wird von einem System aus Methylhydrazin, einer Base und dem Organokatalysator 1 katalysiert. Biologisch attraktive Epoxide 2 mit tetrasubstituiertem trifluormethyliertem Kohlenstoffzentrum wurden mit exzellenter Enantioselektivität erhalten. 18O-Markierungsexperimente deuten darauf hin, dass bei der Reaktion molekularer Sauerstoff aktiviert wird. MTBE=Methyl-tert-butylether.
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- 12We sincerely acknowledge one of the reviewers on our manuscript for his/her smart suggestion concerning mechanism of our oxidation system.
- 13The base is indispensable for this oxidation since no reaction was observed in the absence of base (entry 3, Table 1).
- 14Although a catalytic amount of base is enough for this oxidation (entry 24, Table 1), we used a stoichiometric amount of base because of the shorter reaction time and higher chemical yields. This could be explained by a poor solubility of base in organic solvent.
- 15It should be noted that this hydrazine-induced aerobic epoxidation is not only applicable to trifluoromethyl-disubstituted enones, but also to nonfluorinated disubstituted enones, that is, aerobic epoxidation of the nonfluorinated analogue of 1 a, (Z)-1,3-diphenylbut-2-en-1-one, in the presence of 4 a (5 mol %), H2NNHMe (3.0 equiv), and Cs2CO3 (3.0 equiv) in MTBE gave the nonfluorinated analogue of 3 a, ((2S,3R)-3-methyl-3-phenyloxiran-2-yl)(phenyl)methanone, in 71 % yield as a major isomer (d.r.=73:27), though no enantioselectivity was observed (6 % ee).
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