Carboxylate-Directed Oxidative Annulation via C(Alkenyl)−H Activation/Double Alkyne Insertion/1,4-Pd Migration: Synthesis of Functionalized Naphthalenes

Cheng Hao Fu; Manjaly J. Ajitha; Veerabhushanam Kadiyala; Yu Chun Wang; Tzu Yu Hsu; I. Hsuan Sung; Kuo Wei Huang; Chih Ming Chou

doi:10.1002/adsc.202400973

Carboxylate-Directed Oxidative Annulation via C(Alkenyl)−H Activation/Double Alkyne Insertion/1,4-Pd Migration: Synthesis of Functionalized Naphthalenes

Cheng Hao Fu, Manjaly J. Ajitha, Veerabhushanam Kadiyala, Yu Chun Wang, Tzu Yu Hsu, I. Hsuan Sung, Kuo Wei Huang^*, Chih Ming Chou^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

A palladium-catalyzed double consecutive C(alkenyl)−H activation/alkyne insertion method utilizing a free carboxylic acid as a directing group in the preparation of functionalized naphthalenes is reported. The reaction mechanism involves a sequence of the C (alkenyl)−H activation/alkyne insertion/1,4-palladium migration/reductive elimination steps. The second alkyne insertion occurred at the phenyl ring of the intermediate generated from the first alkyne insertion via 1,4-palladium migration, which is an uncommon case in typical C−H activation/alkyne insertion chemistry, providing functionalized naphthalene products. Additionally, the kinetic studies and control experiments as well as density functional theory (DFT) studies are also investigated to elucidate the reaction mechanism.

Original language	English (US)
Journal	Advanced Synthesis and Catalysis
DOIs	https://doi.org/10.1002/adsc.202400973
State	Accepted/In press - 2024

Keywords

1,4-palladium migration
Alkyne insertion
C(alkenyl)−H activation
DFT
Palladium-catalyzed

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/adsc.202400973

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@article{807ab0fa69054c47b412890d93d7a5f3,

title = "Carboxylate-Directed Oxidative Annulation via C(Alkenyl)−H Activation/Double Alkyne Insertion/1,4-Pd Migration: Synthesis of Functionalized Naphthalenes",

abstract = "A palladium-catalyzed double consecutive C(alkenyl)−H activation/alkyne insertion method utilizing a free carboxylic acid as a directing group in the preparation of functionalized naphthalenes is reported. The reaction mechanism involves a sequence of the C (alkenyl)−H activation/alkyne insertion/1,4-palladium migration/reductive elimination steps. The second alkyne insertion occurred at the phenyl ring of the intermediate generated from the first alkyne insertion via 1,4-palladium migration, which is an uncommon case in typical C−H activation/alkyne insertion chemistry, providing functionalized naphthalene products. Additionally, the kinetic studies and control experiments as well as density functional theory (DFT) studies are also investigated to elucidate the reaction mechanism.",

keywords = "1,4-palladium migration, Alkyne insertion, C(alkenyl)−H activation, DFT, Palladium-catalyzed",

author = "Fu, {Cheng Hao} and Ajitha, {Manjaly J.} and Veerabhushanam Kadiyala and Wang, {Yu Chun} and Hsu, {Tzu Yu} and Sung, {I. Hsuan} and Huang, {Kuo Wei} and Chou, {Chih Ming}",

note = "Publisher Copyright: {\textcopyright} 2024 Wiley-VCH GmbH.",

year = "2024",

doi = "10.1002/adsc.202400973",

language = "English (US)",

journal = "Advanced Synthesis and Catalysis",

issn = "1615-4150",

publisher = "Wiley",

}

TY - JOUR

T1 - Carboxylate-Directed Oxidative Annulation via C(Alkenyl)−H Activation/Double Alkyne Insertion/1,4-Pd Migration

T2 - Synthesis of Functionalized Naphthalenes

AU - Fu, Cheng Hao

AU - Ajitha, Manjaly J.

AU - Kadiyala, Veerabhushanam

AU - Wang, Yu Chun

AU - Hsu, Tzu Yu

AU - Sung, I. Hsuan

AU - Huang, Kuo Wei

AU - Chou, Chih Ming

PY - 2024

Y1 - 2024

N2 - A palladium-catalyzed double consecutive C(alkenyl)−H activation/alkyne insertion method utilizing a free carboxylic acid as a directing group in the preparation of functionalized naphthalenes is reported. The reaction mechanism involves a sequence of the C (alkenyl)−H activation/alkyne insertion/1,4-palladium migration/reductive elimination steps. The second alkyne insertion occurred at the phenyl ring of the intermediate generated from the first alkyne insertion via 1,4-palladium migration, which is an uncommon case in typical C−H activation/alkyne insertion chemistry, providing functionalized naphthalene products. Additionally, the kinetic studies and control experiments as well as density functional theory (DFT) studies are also investigated to elucidate the reaction mechanism.

AB - A palladium-catalyzed double consecutive C(alkenyl)−H activation/alkyne insertion method utilizing a free carboxylic acid as a directing group in the preparation of functionalized naphthalenes is reported. The reaction mechanism involves a sequence of the C (alkenyl)−H activation/alkyne insertion/1,4-palladium migration/reductive elimination steps. The second alkyne insertion occurred at the phenyl ring of the intermediate generated from the first alkyne insertion via 1,4-palladium migration, which is an uncommon case in typical C−H activation/alkyne insertion chemistry, providing functionalized naphthalene products. Additionally, the kinetic studies and control experiments as well as density functional theory (DFT) studies are also investigated to elucidate the reaction mechanism.

KW - 1,4-palladium migration

KW - Alkyne insertion

KW - C(alkenyl)−H activation

KW - DFT

KW - Palladium-catalyzed

UR - http://www.scopus.com/inward/record.url?scp=85209769728&partnerID=8YFLogxK

U2 - 10.1002/adsc.202400973

DO - 10.1002/adsc.202400973

M3 - Article

AN - SCOPUS:85209769728

SN - 1615-4150

JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

ER -

Carboxylate-Directed Oxidative Annulation via C(Alkenyl)−H Activation/Double Alkyne Insertion/1,4-Pd Migration: Synthesis of Functionalized Naphthalenes

Abstract

Keywords

ASJC Scopus subject areas

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