Dearomative 1,4-difunctionalization of naphthalenes via palladium-catalyzed tandem Heck/Suzuki coupling reaction

Bo Zhou, Hongliang Wang, Zhong-Yan Cao, Jia-Wen Zhu, Ren-Xiao Liang, Xin Hong () and Yi-Xia Jia ()
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Bo Zhou: Zhejiang University of Technology
Hongliang Wang: Zhejiang University
Zhong-Yan Cao: Zhejiang University of Technology
Jia-Wen Zhu: Zhejiang University of Technology
Ren-Xiao Liang: Zhejiang University of Technology
Xin Hong: Zhejiang University
Yi-Xia Jia: Zhejiang University of Technology

Nature Communications, 2020, vol. 11, issue 1, 1-10

Abstract: Abstract Dearomative functionalization reactions represent an important strategy for the synthesis of valuable three-dimensional molecules from simple planar aromatics. Naphthalene is a challenging arene towards transition-metal-catalyzed dearomative difunctionalization reactions. Reported herein is an application of naphthalene as a masked conjugated diene in a palladium-catalyzed dearomative 1,4-diarylation or 1,4-vinylarylation reaction via tandem Heck/Suzuki sequence. Three types of 1,4-dihydronaphthalene-based spirocyclic compounds are achieved in excellent regio- and diastereoselectivities. Key to this transformation is the inhibition of a few competitive side reactions, including intramolecular naphthalenyl C-H arylation, intermolecular Suzuki cross-coupling, dearomative 1,2-difunctionalization, and dearomative reductive-Heck reaction. Density functional theory (DFT) calculations imply that the facile exergonic dearomative insertion of a naphthalene double bond disrupts the sequence of direct Suzuki coupling, leading to the tandem Heck/Suzuki coupling reaction. The observed regioselectivity towards 1,4-difunctionalization is due to the steric repulsions between the introduced aryl group and the spiro-scaffold in 1,2-difunctionalization.

Date: 2020
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DOI: 10.1038/s41467-020-18137-w

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