ChemInform Abstract: Pinpoint‐Fluorinated Phenanthrene Synthesis Based on C—F Bond Activation of Difluoroalkenes.

Fuchibe, Kohei; Morikawa, Toshiyuki; Ueda, Rikizo; Okauchi, Tatsuo; Ichikawa, Junji

doi:10.1002/chin.201611117

Cited by 2 publications

(3 citation statements)

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“…Phenacenes are an important and versatile subclass of polycyclic aromatic hydrocarbons (PAHs) which can serve as organic semiconducting materials. 858 In the presence of a cationic Pd(II) catalyst, gem-difluoroalkenes such 1,1-difluoro-1-alkenes 859,860 or 1,1,2-trifluoro-1-alkenes 861 can undergo electrophilic Friedel−Crafts-type cyclizations to synthesize a broad array of highly appealing pinpoint-fluorinated phenanthrenes (Scheme 546a) or phenacenes (Scheme 546b). Mechanistically, the Pd catalyst first coordinated to the trifluoroalkene to form a π-complex.…”

Section: Photoredox Catalysismentioning

confidence: 99%

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

et al. 2022

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Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, and advanced materials. Significant efforts have been made toward the development of new and practical methods to access this important class of compounds by selectively activating the alkenyl C(sp2)–H bonds in recent years. In this comprehensive review, we describe the state-of-the-art strategies for the direct functionalization of alkenyl sp2 C–H and C–F bonds until June 2022. Moreover, metal-free, photoredox, and electrochemical strategies are also covered. For clarity, this review has been divided into two parts; the first part focuses on currently available alkenyl sp2 C–H functionalization methods using different alkene derivatives as the starting materials, and the second part describes the alkenyl sp2 C–F bond functionalization using easily accessible gem-difluoroalkenes as the starting material. This review includes the scope, limitations, mechanistic studies, stereoselective control (using directing groups as well as metal-migration strategies), and their applications to complex molecule synthesis where appropriate. Overall, this comprehensive review aims to document the considerable advancements, current status, and emerging work by critically summarizing the contributions of researchers working in this fascinating area and is expected to stimulate novel, innovative, and broadly applicable strategies for alkenyl sp2 C–H and C–F bond functionalizations in the coming years.

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Section: Photoredox Catalysismentioning

confidence: 99%

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

et al. 2022

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“…In the first step, 1,3-dimethoxybenzene (10) was lithiated with BuLi and subsequently formylated using N,Ndimethylformamide (DMF). 32 Cleavage of the resulting 2,6-dimethoxybenzaldehyde (11) under mild reaction conditions using excess aluminum chloride at room temperature gave DHBA in moderate yield (Scheme 1). 34 The 2,6-dihydroxybenzaldehyde aroylhydrazones 1−8 and alkanoylhydrazone 9 were prepared via the condensation of DHBA with the corresponding hydrazides in boiling ethanol (Scheme 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…31 2,6-Dimethoxybenzaldehyde (11). 32 To a solution of 1,3dimethoxybenzene (10, 5.54 g, 40.1 mmol) in THF (15 mL) was added a solution of n-BuLi in hexane (30 mL, 1.6 mol/L, 48.0 mmol) at 0 °C over 20 min. The reaction mixture was stirred at rt for 30 min and again cooled to 0 °C, and DMF (3.7 mL, 48 mmol) was added dropwise.…”

Section: ■ Experimental Proceduresmentioning

confidence: 99%

2,6-Dihydroxybenzaldehyde Analogues of the Iron Chelator Salicylaldehyde Isonicotinoyl Hydrazone: Increased Hydrolytic Stability and Cytoprotective Activity against Oxidative Stress

Jansová

Kubeš

Reimerová

et al. 2018

Chem. Res. Toxicol.

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Salicylaldehyde isonicotinoyl hydrazone (SIH) is a small molecule and lipophilic chelating agent that firmly binds ferric ions from the cellular labile iron pool and is able to protect various tissues against oxidative damage. Previously, SIH possessed the best ratio of cytoprotective efficiency to toxicity among various iron chelators, including the desferrioxamine, deferiprone, and deferasirox used in clinical practice. Here, we prepared a series of 2,6-dihydroxybenzaldehyde aroylhydrazones as SIH analogues with an additional hydroxyl group that can be involved in the chelation of metal ions. Compound JK-31 (2,6-dihydroxybenzaldehyde 4-chlorobenzohydrazone) showed the best cytoprotective efficiency among the studied compounds including SIH. This compound significantly protected H9c2 cardiomyoblast cells against oxidative stress induced by various pro-oxidants, such as hydrogen peroxide, tert-butyl hydroperoxide, paraquat, epinephrine, N-acetyl-p-benzoquinone imine (a toxic metabolite of paracetamol), and 6-hydroxydopamine. The exceptional cytoprotective activity of JK-31 was confirmed using epifluorescence microscopy, where JK-31-treated H9c2 cells maintained a higher mitochondrial inner membrane potential in the presence of a lethal dose of hydrogen peroxide than was observed with cells treated with SIH. Hence, this study demonstrates the deleterious role of free iron ions in oxidative injury and the potential of 2,6-dihydroxybenzaldehyde aroylhydrazones in the prevention of various types of cardiac injuries, highlighting the need for further investigations into these compounds.

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ChemInform Abstract: Pinpoint‐Fluorinated Phenanthrene Synthesis Based on C—F Bond Activation of Difluoroalkenes.

Cited by 2 publications

References 1 publication

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

2,6-Dihydroxybenzaldehyde Analogues of the Iron Chelator Salicylaldehyde Isonicotinoyl Hydrazone: Increased Hydrolytic Stability and Cytoprotective Activity against Oxidative Stress

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ChemInform Abstract: Pinpoint‐Fluorinated Phenanthrene Synthesis Based on C—F Bond Activation of Difluoroalkenes.

Cited by 2 publications

References 1 publication

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

2,6-Dihydroxybenzaldehyde Analogues of the Iron Chelator Salicylaldehyde Isonicotinoyl Hydrazone: Increased Hydrolytic Stability and Cytoprotective Activity against Oxidative Stress

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Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications