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Intramolecular Hiyama Coupling: Synthesis of 1,8,13-Trisubstituted Chiral Triptycenes with Three Different Substituents by Intramolecular Substituent Transfer.

Takayuki IwataMasato HanadaSatoru KumagaiTatsuro YoshinagaYoshihito ShiotaKazunari YoshizawaMitsuru Shindo
Published in: Chemistry (Weinheim an der Bergstrasse, Germany) (2023)
Herein, we describe Hiyama coupling via intramolecular substituent transfer from silicon on one blade of triptycenes to another to yield 1,8,13-trisubstituted chiral triptycenes. This reaction is attributed to the proximity effect of substituents on triptycene, which plays an important role in not only the formation of the oxy-palladacycle but also the activation of the silyl group to facilitate σ-bond metathesis. After bromination and nucleophilic ring opening, the second intramolecular Hiyama coupling provided various 1,8,13-trisubstituted chiral triptycenes. The optical resolution of 1,8,13-triptycene afforded an optically active form for the first time.
Keyphrases
  • electron transfer
  • energy transfer
  • room temperature
  • capillary electrophoresis
  • ionic liquid
  • mass spectrometry
  • high resolution
  • single molecule