Title: Intramolecular Hiyama Coupling: Synthesis of 1,8,13‐Trisubstituted Chiral Triptycenes with Three Different Substituents by Intramolecular Substituent Transfer.
Authors: Iwata, Takayuki; Hanada, Masato; Kumagai, Satoru; Yoshinaga, Tatsuro; Shiota, Yoshihito; Yoshizawa, Kazunari; Shindo, Mitsuru
Abstract: 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.
Subjects: TRIPTYCENES; OPTICAL resolution; SILYL group; METATHESIS reactions; METATHESIS (Linguistics)
Publication: Chemistry - A European Journal, 2023, Vol 29, Issue 39, p1
ISSN: 0947-6539
Publication type: Academic Journal
DOI: 10.1002/chem.202300988

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

Iwata, Takayuki; Hanada, Masato; Kumagai, Satoru; Yoshinaga, Tatsuro; Shiota, Yoshihito; Yoshizawa, Kazunari; Shindo, Mitsuru