Reactions of 5,6-Dilithioacenaphthene-N-N,N′,N′-Tetramethyl-1,2-ethanediamine Complex with α-Diketones. II. Competitive Oxophilic and Carbophilic Additions and Redox Reactions

Tanaka, Norio; Kasai, T.

doi:10.1246/bcsj.54.3026

Cited by 12 publications

(11 citation statements)

References 42 publications

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“…Previous work undertaken on analogous naphthalene18 and acenaphthene17 compounds highlighted 5,6‐dibromoacenaphthylene 13 28,29 as a potential starting material for the preparation of chalcogen‐substituted acenaphthylenes 1–12 . 1,8‐Dibromonaphthalene N13 and 5,6‐dibromoacenaphthene A13 both readily undergo lithium–halogen exchange reactions to form mono‐ and dilithiated precursors for many metal‐substitution reactions, and have previously been shown to react with diphenyl dichalcogenides to form substituted chalcogen compounds 17,18,30,31…”

Section: Resultsmentioning

confidence: 99%

“…The isotopic distribution patterns of the respective fragment ions were confirmed using IsoPro 3.1 MS simulation software;43 however, in each case only the most abundant isotopic peak for each fragment ion is reported. Acenaphthene precursors ( A1 – A12 ,17 5,6‐dibromoacenaphthene A13 20 and 5,6‐diiodoacenaphthene A14 )30 were prepared following standard literature procedures.…”

Section: Methodsmentioning

confidence: 99%

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Computational and Experimental Insight into the Molecular Mechanism of Carboxamide Inhibitors of Succinate‐Ubquinone Oxidoreductase

Zhu

et al. 2014

ChemMedChem

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Succinate-ubiquinone oxidoreductase (SQR, EC 1.3.5.1), also known as mitochondrial respiratory complex II or succinate dehydrogenase (SDH), catalyzes the oxidation of succinate to fumarate as part of the tricarboxylic acid cycle. SQR has been identified as a novel target of a large family of agricultural fungicides. However, the detailed mechanism of action between the fungicides and SQR is still unclear, and the bioactive conformation of fungicides in the SQR binding pocket has not been identified. In this study, the kinetics of porcine SQR inhibition by ten commercial carboxamide fungicides were measured, and noncompetitive inhibition was observed with respect to succinate, DCIP, and cytochrome c, while competitive inhibition was observed with respect to ubiquinone. With the aim to uncover the binding conformation of these fungicides, molecular docking, molecular dynamics simulation, and molecular mechanics/Poisson-Boltzmann surface area (MM/PBSA) calculations were then performed. The excellent correlation (r(2) =0.94) between the calculated (ΔGcal ) and experimental (ΔGexp ) binding free energies indicates that the obtained docking conformation could be the bioactive conformation. The acid moiety of carboxamide fungicides inserts into the ubiquinone binding site (Q-site) of SQR, forming van der Waals (vdW) interactions with C_R46, C_S42, B_I218, and B_P169, while the amine moiety extends to the mouth of the Q-site, forming vdW interactions with C_W35, C_I43, and C_I30. The carbonyl oxygen atom of the carboxamide forms hydrogen bonds with B_W173 and D_Y91. These findings provide valuable information for the design of more potent and specific inhibitors of SQR.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Computational and Experimental Insight into the Molecular Mechanism of Carboxamide Inhibitors of Succinate‐Ubquinone Oxidoreductase

Zhu

et al. 2014

ChemMedChem

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“…1,8-dibromonaphthalene N13 and 5,6-dibromoacenaphthene A13 both readily undergo lithium-halogen exchange reactions to form mono-and di-lithiated precursors for many metal-substitution reactions, and have previously been shown to react with diphenyl dichalcogenides to form substituted chalcogen compounds. [17,18,30,31] 13 was initially prepared following a modified version of the route reported by Meinwald and Chiang. [28] A chloroform solution of 5,6-dibromoacenaphthene A13 [32] was treated with 2.2 equivalents of N-bromosuccinimide (NBS) and 0.22 equivalents of benzoyl peroxide and heated under reflux for five hours affording A0 (yield 74%).…”

Section: ]mentioning

confidence: 99%

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

et al. 2014

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Keywords: acenaphthylene /peri-substitution /3c-4e interaction /X-ray crystallography / DFT calculations/non-covalent A series of peri-substituted acenaphthylenes containing mixed halogen-chalcogen functionalities at the 5,6-positions in 1-6 (Acenapyl [X][EPh] (Acenap = acenaphthylene-5,6-diyl; X = Br, I; E = S, Se, Te) and chalcogen-chalcogen moieties in 7-11 (Acenap [EPh][E`Ph] (Acenap = acenaphthene-5,6-diyl; E/E` = S, Se, Te), have been prepared from their corresponding acenaphthene analogues A1-A11, utilizing 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) for the dehydrogenation of the ethane backbone. The related dihalide compounds 13 and 14 Acenapyl[XX`] (XX` = BrBr, II) have also been prepared following a similar procedure and 1,2,5,6-tetrabromo-1,2-dihydroacenaphthylene A0 was prepared as an intermediate following an alternative route to 13. The series of acenaphthylene compounds have remarkably similar molecular structures to their acenaphthene counterparts, exhibiting an expected increase in periseparation as heavier congeners occupy the close peri-positions.The presence of the ethene bridge, however, naturally compresses the nearest bay angle whilst increasing the splay of the exocyclic peri-atoms, resulting in a minor increase in separation compared with equivalent acenaphthenes. The structures of 1-11, 13 and 14 are discussed and compared with previously reported analogous naphthalene and acenaphthene compounds. Similar to acenaphthene derivatives, aromatic ring conformations and the location of p-type lone-pairs influences the geometry of the peri-region. Under appropriate geometric conditions quasi-linear three-body C Ph -E···Z (E = Te, Se, S; Z = Br/E) fragments provide an attractive component for the E···Z interaction. DFT studies confirm the onset of formation of threecenter, four-electron bonding, similar in extent as observed in analogous acenaphthenes, despite an increase in the peridistances. IntroductionUnderstanding how atoms interact in different bonding situations and the ability to quantify the extent of bonding between two atoms is an ongoing challenge for chemists, and one which dates back to the origins of the electronic theory of valence proposed by Lewis and Langmuir in the early 1900s. [1,2] The stability of molecules was originally ascribed to their ability to pair valence electrons off in chemical bonds to achieve 'stable octets', with the concept of covalence introduced as 'the number of pairs of electrons an atom can share with its neighbor'. [1][2][3] Ambiguity over the bonding in molecules of heavier main-block elements (period 3 and higher), in which an 'octet expansion' would be required in order to conform to conventional Lewis 2c-2e covalent bonding theory, was thus rationalized by the availability of unfilled low-lying d-orbitals. [1] Langmuir, however, accounted for the legitimacy of the octet rule by suggesting the bonding in these species, termed hypervalent, [4] was now ionic rather than covalent in nature. [2] The advancement of molecular orbital theory in t...

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“…As summarized in Table S1 in the Supporting Information, the absorption and emission peaks of 5 a and 5 c are close to those of the reference compounds 8 and 9, respectively. [38,39] The slow evaporation of the chloroform solution of 5 c allowed the separation of yellow-colored needle-like crystals. The structure obtained by X-ray diffraction confirms the main framework of the perylene as well as the two bis (spirodienone) structures ( Figure 5).…”

Section: Physical Propertiesmentioning

confidence: 99%

Formation of Perylenes by Oxidative Dimerization of Naphthalenes Bearing Radical Sources

et al. 2019

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The introduction of phenol groups at the 1,8‐positions of naphthalene allowed its one‐pot oxidative dimerization and subsequent oxidative cyclization to the perylene structures under mild conditions and upon addition of iron (III) chloride. Examination using various derivatives and DFT calculations revealed that these reactions are initiated by the oxidation of the phenol moiety to generate a radical cation, which is supplied as a radical source for the reactions. The delocalization of the spin density from the radical cation of the introduced phenol groups to the naphthalene ring is proposed to be responsible for the intermolecular oxidative homo‐coupling reactions at the peri‐positions of the naphthalene and the subsequent oxidative cyclization at the 8,8’‐positions of the 1,1’‐binaphthyl derivative.

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Reactions of 5,6-Dilithioacenaphthene-N-N,N′,N′-Tetramethyl-1,2-ethanediamine Complex with α-Diketones. II. Competitive Oxophilic and Carbophilic Additions and Redox Reactions

Cited by 12 publications

References 42 publications

Computational and Experimental Insight into the Molecular Mechanism of Carboxamide Inhibitors of Succinate‐Ubquinone Oxidoreductase

Computational and Experimental Insight into the Molecular Mechanism of Carboxamide Inhibitors of Succinate‐Ubquinone Oxidoreductase

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

Formation of Perylenes by Oxidative Dimerization of Naphthalenes Bearing Radical Sources

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