Domino Synthesis of Fluorine‐Substituted Polycyclic Aromatic Hydrocarbons: 1,1‐Difluoroallenes as Synthetic Platforms

Fuchibe, Kohei; Mayumi, Yuka; Zhao, Nan; Watanabe, Shumpei; Misaki, Yohji; Ichikawa, Junji

doi:10.1002/ange.201302740

Cited by 24 publications

(7 citation statements)

References 58 publications

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“…While using 1-(trifluoromethyl)alkenes (1, R = (hetero)aryl) such as 1w-1x as substrates, C-Cu bond formation may be electronically favored at the benzylic position stabilization by the (hetero)aryl group (C 0 ). [57][58][59][60][61][62] After further enantioselective formation of intermediate D, cis b-F elimination [33][34][35][36][37][38][39][40][45][46][47][48][49] delivers the final product 3 and a CuF-like species E, which can undergo anion exchange with NaO t Bu to regenerate the copper catalyst.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Copper-Catalyzed Asymmetric Defluoroborylation of 1-(Trifluoromethyl)Alkenes

Gao

Yuan

Zhao

et al. 2018

Chem

147

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gem-Difluoroalkenes have steric and electronic profiles similar to those of ketones, aldehydes, and esters, and consequently have been used widely as carbonyl isosteres in modern drug discovery. Although many attempts have been made to achieve gem-difluoroalkenes, the induction of enantioselectivity at the a position of a gem-difluorovinyl group still remains a challenge. Herein, an efficient method for the construction of gem-difluoroallylboronates with high enantiomeric excess via a copper-catalyzed defluoroborylation of 1-(trifluoromethyl)alkenes with B 2 pin 2 is described. The reaction conditions were mild, and a variety of common functional groups, such as ether, fluoride, chloride, bromide, iodide, ester, cyano, sulfide, amino, and indoyl groups, were well tolerated. Furthermore, we not only applied this developed system as a powerful synthetic tool for the late-stage modification of complex compounds but also highlighted the utility of the formed compounds in synthesis.

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Section: Resultsmentioning

confidence: 99%

“…Defluorinative functionalization of fluorine-containing compounds has shown promise as it confers synthetic versatility to inert C-F bonds. [33][34][35][36][37][38][39][40] Defluoroborylations of…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Asymmetric Defluoroborylation of 1-(Trifluoromethyl)Alkenes

Gao

Yuan

Zhao

et al. 2018

Chem

147

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“…Electron-rich as well as electron-poor substrates underwent the transformation. The presence of halogen substituents [Cl (16, and 23), F (18, 19, 20, 22, and 25)], ethers [OCH 3 (15), SCH 3 (26)], amides [CONEt 2 (10)], and acids [COOH (24)] were tolerated. For the synthesis of 13, 14, and 15, a larger excess of base (conditions b) was required, whereas for the chlorinesubstituted product, 16, four equivalents (conditions c) were enough to observe full conversion.…”

Section: Resultsmentioning

confidence: 99%

“…However, allylic trifluoromethyl13 and difluoromethyl groups14 display a lower activation barrier and can undergo substitution with carbon and nitrogen nucleophiles through a S N 2′ mechanism. For instance, difluoroallenes15 and β,β‐difluorostyrenes16 were reported to be versatile substrates for the preparation of fluorine‐substituted PAHs and 3‐fluorinated isoquinolines.…”

Section: Introductionmentioning

confidence: 99%

A Transition‐Metal‐Free Synthesis of Fluorinated Naphthols

Hammann

Unzner

Magauer

2014

Chemistry A European J

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Herein, we describe a transition-metal-free protocol for the conversion of simple 2-allyl-3-(trifluoromethyl)phenols into substituted 5-fluoronaphthalen-1-ols. The key events of this reaction include the selective activation of two C-F bonds and formation of an intermediate hexatriene system, which undergoes a 6π electrocyclization, followed by rearomatization. This concept enables the rapid conversion (three steps) of various commercially available 3-(trifluoromethyl)phenols into novel fluorine-containing naphthols, which are difficult to prepare by previous methods. The reported sequence was also extended to a one-pot transformation of 3-(trifluoromethyl)phenols into 5-fluoronaphthalen-1-ols.

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“…The recent discovery of effective intramolecular aryl-aryl coupling via C-F bond activation under transition-metal free conditions might be a solution to this problem. Recently, Siegel et al [21], Ichikawa et al [22], and Amsharov et al [23,24] have demonstrated the efficiency of the C─F bond activation strategy for the synthesis of various bowl-shaped PAHs via formal HF elimination step (cyclodehydrofluorination). In the last case, the effective cyclization was achieved utilizing easily accessible aluminum oxide, which makes the approach highly attractive for preparative-scale synthesis.…”

Section: Wet-chemical Synthesismentioning

confidence: 99%

Rational Synthesis of Fullerenes

Amsharov¹

2018

Fullerenes and Relative Materials - Properties and Applications

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Fullerenes are a unique family of carbon-based cage molecules, which attract interest because of their remarkable properties and potential applications. Most effort so far has been focused on the study of C 60 and C 70 , whereas other members of the huge fullerene family remain poorly explored. One of the main challenges in this field is the developing of the synthetic methods, which are suitable for the production of these unique materials in isomer-pure form in macroscopic amounts. Here, we review studies toward the rational synthesis of fullerenes from molecular precursors that have been published to date. The scope and limitation of the zipping strategy are discussed. The relevance and prospects for construction of the fullerene cages and related carbon-based nanostructures via cyclodehydrofluorination (C─F bond activation) are highlighted.

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Domino Synthesis of Fluorine‐Substituted Polycyclic Aromatic Hydrocarbons: 1,1‐Difluoroallenes as Synthetic Platforms

Cited by 24 publications

References 58 publications

Copper-Catalyzed Asymmetric Defluoroborylation of 1-(Trifluoromethyl)Alkenes

Copper-Catalyzed Asymmetric Defluoroborylation of 1-(Trifluoromethyl)Alkenes

A Transition‐Metal‐Free Synthesis of Fluorinated Naphthols

Rational Synthesis of Fullerenes

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