Catalytic and Enantioselective Synthesis of Chiral Multisubstituted Tribenzothiepins by Intermolecular Cycloadditions

Yu Ki Tahara, Riku Matsubara, Akihito Mitake, Tatsuki Sato, Stephen Kyalo Kanyiva, Takanori Shibata

Research output: Contribution to journalArticle

7 Citations (Scopus)

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 eevalues 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.

Original languageEnglish
JournalAngewandte Chemie - International Edition
DOIs
Publication statusAccepted/In press - 2016

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Diynes
Cycloaddition
Derivatives
Heating
Molecules
Kinetics
Sulfides

Keywords

  • Chirality
  • Cycloaddition
  • Enantioselectivity
  • Rhodium
  • Synthetic methods

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

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AU - Tahara, Yu Ki

AU - Matsubara, Riku

AU - Mitake, Akihito

AU - Sato, Tatsuki

AU - Kanyiva, Stephen Kyalo

AU - Shibata, Takanori

PY - 2016

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AB - 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 eevalues 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.

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KW - Rhodium

KW - Synthetic methods

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