CF Bond Activation of Unactivated Aliphatic Fluorides: Synthesis of Fluoromethyl-3,5-diaryl-2-oxazolidinones by Desymmetrization of 2-Aryl-1,3-difluoropropan-2-ols†
Corresponding Author
Prof. Dr. Günter Haufe
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster (Germany)
Günter Haufe, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster (Germany)
Norio Shibata, Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorSatoru Suzuki
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorHiroyuki Yasui
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorChisato Terada
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorTakashi Kitayama
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorDr. Motoo Shiro
Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Norio Shibata
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Günter Haufe, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster (Germany)
Norio Shibata, Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Günter Haufe
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster (Germany)
Günter Haufe, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster (Germany)
Norio Shibata, Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorSatoru Suzuki
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorHiroyuki Yasui
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorChisato Terada
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorTakashi Kitayama
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Search for more papers by this authorDr. Motoo Shiro
Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Norio Shibata
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
Günter Haufe, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster (Germany)
Norio Shibata, Department of Frontier Materials, 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 MEXT (Ministry of Education, Culture, Sports, Science and Technology) (24105513, Project No. 2304: Advanced Molecular Transformation by Organocatalysts) and by the Deutsche Forschungsgemeinschaft (DFG). We thank the Asahi Glass Foundation for partial support.
Graphical Abstract
How to lose fluorine: Biologically relevant oxazolidinones 1 were synthesized through the desymmetrization of unactivated aliphatic difluorides by Si-induced catalytic CF bond-cleavage using BSA/CsF (BSA=bis(trimethylsilyl)acetamide). The direct transformation of 2 with isocyanates into 1 by cascade carbamoylation/cyclization, in which cyclization is induced by Na-assisted CF bond activation, was also achieved.
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