Synthesis of Benzofulvenes via Cp*Co(III)-Catalyzed C–H Activation and Carbocyclization of Aromatic Ketones with Internal Alkynes

Yu, Yongqi; Wu, Qianlong; Liu, Da; Hu, Liang; Lin, Ying‐Chu; Tan, Ze; Zhu, Gangguo

doi:10.1021/acs.joc.9b00595

Cited by 22 publications

(6 citation statements)

References 85 publications

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“…Recently, with growing interest of ketone as directing group for the site-selective C–H bond functionalizations under high-valent cobalt catalysis, Tan and co-workers disclosed an elegant report on the synthesis of benzofulvenes via ketone-directed C–H bond alkenylation/nucleophilic-addition/dehydration cascade (Scheme ). The protocol displayed a wide scope of aryl ketones with good tolerance of functional groups. Unfortunately, terminal alkynes and bis -aliphatic internal alkynes did not furnish the desired products.…”

Section: Ketone-directed C–h Bond Functionalizationsmentioning

confidence: 99%

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Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

2022

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Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, and they are in high demand. This will be a cause of concern, and hence, it is important to develop methods based on 3d metals, which are widely present in the Earth’s crust. In this regard, the use of 3d metal catalysts or their precursors for catalysis, in general, and C–H bond functionalizations, in particular, has gained significant momentum in the recent times. The major development in catalytic C–H bond functionalizations with 3d metals has been achieved predominantly with strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, and 8-amino-quinolinyl groups. Thus, prefunctionalization of substrates with these directing groups is necessary, which contradicts the step- and atom-economy of C–H bond activation. However, commonly available functional groups such as aldehyde, ketone, carboxylic acid, amide, hydroxy, and N-oxides loosely bind to metals through weak-coordination. These weakly coordinating directing groups orient the metal to activate C–H bond regioselectively without the need for preinstalled strongly coordinating directing groups. Although it is challenging, this contemporary topic has been actively pursued by many researchers in recent times. Through this article, we provide a comprehensive overview of 3d metal-catalyzed, weakly coordinating, directing-group-enabled C–H bond functionalizations reported until March 2021.

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Section: Ketone-directed C–h Bond Functionalizationsmentioning

confidence: 99%

“…nucleophilic-addition/dehydration cascade (Scheme 94). 191 The protocol displayed a wide scope of aryl ketones with good tolerance of functional groups. Unfortunately, terminal alkynes and bis-aliphatic internal alkynes did not furnish the desired products.…”

Section: Ketone-directed C−h Bond Functionalizationsmentioning

confidence: 99%

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

2022

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“…[51,52] In this regard, Silicon phosphide (SiP) has been investigated by several group due to its high stability, large bandgap, strong anisotropy, and fast photoresponse. Recently, Yu et al [53] have successfully prepared monolayer SiP for the first time using the chemical vapor transport method. The as-synthesized material exhibits high responsiveness and reasonable repetition period when employed for photodetector application.…”

Section: Introductionmentioning

confidence: 99%

Point Defects in Hexagonal SiP Monolayer: A Systematic Investigation on the Electronic and Magnetic Properties

Ha,

Ponce‐Pérez,

Guerrero‐Sanchez

et al. 2024

Advcd Theory and Sims

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In this work, point defects are proposed to modify the electronic and magnetic properties of SiP monolayer. Pristine monolayer is a non‐magnetic semiconductor 2D material with energy gap of 1.52(2.21) eV as predicted by PBE(HSE06) functional. Single Si vacancy (), Si+P divacancy (), and substituting one P atom by one Si atom () magnetize significantly SiP monolayer. Herein, total magnetic moments between 1.00 and 2.00 are obtained . In contrast, no magnetism is induced by single P vacancy (), substituting one Si atom by one P atom (), and exchanging pair Si‐P positions (). Moreover, significant magnetization of SiP monolayer is also achieved by doping with single Li and Cu atoms ( and ), as well as pair of Li and Cu atoms ( and ). Total magnetic moments between 0.84 and 1.42 are obtained. Interestingly, the half‐metallicity is observed in and systems. When substituting P atom, F, Cl, and Br impurities reduce significantly the SiP monolayer bandgap, preserving its non‐magnetic nature. In contrast, a total magnetic moment of 1.26 is obtained by doping with I atom. Results presented herein may introduce the defected and doped SiP systems as prospective 2D candidates for spintronic and optoelectronic applications.

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“…The first merged photocatalytic pathway for the C–O cross-coupled esterification of carboxylic acids to α-acyloxy ketones was demonstrated in 2023 (Scheme , d) . Photochemistry shares an equally important role in green synthesis compared to electrochemistry and yet studies about photocatalytic direct α-oxidation of ketones are not seen much due to their relatively weak coordination capability . Hence, it is highly desirable and of great importance to seek a more efficient and green synthetic method for α-acyloxy ketones.…”

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confidence: 99%

The O₂-Mediated Cross-Dehydrogenative Coupling: Rose Bengal-Catalyzed Direct Oxidative α-Acyloxylation of Ketones

et al. 2023

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A general and facile approach for the direct oxidative α-acyloxylation of ketones using molecular oxygen as the oxidant is developed. This method avoids the use of excessive peroxides and expensive metal catalysts, affording a variety of αacyloxylated ketones in satisfactory yields. Experimental studies indicate that the reaction proceeds via a radical pathway. Additionally, α-hydroxy ketones could be obtained by changing the solvent.

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Synthesis of Benzofulvenes via Cp*Co(III)-Catalyzed C–H Activation and Carbocyclization of Aromatic Ketones with Internal Alkynes

Cited by 22 publications

References 85 publications

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

Point Defects in Hexagonal SiP Monolayer: A Systematic Investigation on the Electronic and Magnetic Properties

The O₂-Mediated Cross-Dehydrogenative Coupling: Rose Bengal-Catalyzed Direct Oxidative α-Acyloxylation of Ketones

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Synthesis of Benzofulvenes via Cp*Co(III)-Catalyzed C–H Activation and Carbocyclization of Aromatic Ketones with Internal Alkynes

Cited by 22 publications

References 85 publications

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

Point Defects in Hexagonal SiP Monolayer: A Systematic Investigation on the Electronic and Magnetic Properties

The O2-Mediated Cross-Dehydrogenative Coupling: Rose Bengal-Catalyzed Direct Oxidative α-Acyloxylation of Ketones

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The O₂-Mediated Cross-Dehydrogenative Coupling: Rose Bengal-Catalyzed Direct Oxidative α-Acyloxylation of Ketones