TY - JOUR
T1 - Quadruple Role of Pd Catalyst in Domino Reaction Involving Aryl to Alkyl 1,5-Pd Migration to Access 1,9-Bridged Triptycenes
AU - Iwata, Takayuki
AU - Kumagai, Satoru
AU - Yoshinaga, Tatsuro
AU - Hanada, Masato
AU - Shiota, Yoshihito
AU - Yoshizawa, Kazunari
AU - Shindo, Mitsuru
N1 - Funding Information:
This work was partially supported by JSPS KAKENHI (Grant No. JP18H02557, JP18H04418, JP18H04624, JP20H04780, JP20K21198, and JP20K15283), NAGASE Science Technology Foundation (M.S.), Asahi Glass Foundation (T.I.), Qdai‐jump Research Program Wakaba Challenge at Kyushu University (T.I.), and the IRCCS Fusion Emergent Research Program (T.I.). This work was performed under the Cooperative Research Program “Network Joint Research Center for Materials and Devices.” We thank Mr. T. Matsumoto at Kyushu University for the X‐ray crystal structure analyses. We are grateful to Prof. K. Tomooka and Dr. K. Igawa at Kyushu University for their help in optical resolution using chiral columns.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/8/11
Y1 - 2021/8/11
N2 - 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 Pd0, PdII and PdIV 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 PdII and stepwise PdIV routes. Asymmetric synthesis of the chiral triptycenes, as well as optical resolution, and further transformation are also reported.
AB - 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 Pd0, PdII and PdIV 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 PdII and stepwise PdIV routes. Asymmetric synthesis of the chiral triptycenes, as well as optical resolution, and further transformation are also reported.
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U2 - 10.1002/chem.202101728
DO - 10.1002/chem.202101728
M3 - Article
C2 - 34125459
AN - SCOPUS:85112297603
VL - 27
SP - 11548
EP - 11553
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 45
ER -