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Quadruple Role of Pd Catalyst in Domino Reaction Involving Aryl to Alkyl 1,5‐Pd Migration to Access 1,9‐Bridged Triptycenes
Author(s) -
Iwata Takayuki,
Kumagai Satoru,
Yoshinaga Tatsuro,
Hanada Masato,
Shiota Yoshihito,
Yoshizawa Kazunari,
Shindo Mitsuru
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101728
Subject(s) - aryl , alkyl , intramolecular force , chemistry , domino , suzuki reaction , phenylboronic acid , catalysis , palladium , medicinal chemistry , cascade reaction , combinatorial chemistry , stereochemistry , organic chemistry
A Pd‐catalyzed domino reaction of 1,8,13‐tribromo‐9‐methoxytriptycenes is reported. Under conventional Suzuki coupling conditions, the triptycenes underwent multiple transformations to give 1,9‐bridged triptycenes. Based on mechanistic investigations, a single Pd catalyst functions as Pd 0 , Pd II and Pd IV species to catalyze four distinct processes: (1) aryl to alkyl 1,5‐Pd migration, (2) intramolecular arylation, (3) homocoupling of phenylboronic acid and (4) Suzuki coupling. DFT calculations revealed that 1,5‐Pd migration likely proceeds via both concerted Pd II and stepwise Pd IV routes. Asymmetric synthesis of the chiral triptycenes, as well as optical resolution, and further transformation are also reported.