Catalytic and Enantioselective Synthesis of Chiral Multisubstituted Tribenzothiepins by Intermolecular Cycloadditions
Yu-ki Tahara
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorRiku Matsubara
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorAkihito Mitake
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorTatsuki Sato
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorDr. Kyalo Stephen Kanyiva
International Center for Science and Engineering Programs (ICSEP), Waseda University, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Takanori Shibata
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
JST, ACT-C, Kawaguchi, Saitama, 332-0012 Japan
Search for more papers by this authorYu-ki Tahara
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorRiku Matsubara
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorAkihito Mitake
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorTatsuki Sato
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorDr. Kyalo Stephen Kanyiva
International Center for Science and Engineering Programs (ICSEP), Waseda University, Shinjuku, Tokyo, 169-8555 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Takanori Shibata
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, 169-8555 Japan
JST, ACT-C, Kawaguchi, Saitama, 332-0012 Japan
Search for more papers by this authorGraphical Abstract
End of the tether: The first catalytic and highly enantioselective synthesis of tribenzothiepin derivatives was achieved. Two types of intermolecular cycloadditions, either using diphenyl-sulfide-tethered diynes or 2-phenyl sulfanylbenzene tethered diynes with a monoalkyne, led to chiral multisubstituted tribenzothiepins in good to excellent ee values under mild reaction conditions. The present protocol was used to prepare a chiral tribenzoselenepin.
Abstract
The first catalytic and highly enantioselective synthesis of tribenzothiepin derivatives was achieved. Two types of intermolecular cycloadditions using either diphenyl-sulfide-tethered diynes or 2-phenyl sulfanylbenzene-tethered diynes with a monoalkyne successfully gave chiral multisubstituted tribenzothiepins in good to excellent ee values under mild conditions. The inversion energy of this saddle-shaped molecule was calculated by measurement of the racemization rate of chiral tribenzothiepins using the Eyring kinetic equation under heating conditions. The present protocol could also be used to prepare a chiral tribenzoselenepin.
Supporting Information
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