Synthesis and reactivity of anthracenyl-substituted arenediynes

Gavvalapalli, Nagarjuna; Ren, Yi; Moore, Jeffrey S.

doi:10.1016/j.tetlet.2015.01.011

Cited by 5 publications

(3 citation statements)

References 26 publications

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“…However, such expansion is impossible for the vinyl radicals derived from alkynes. As a result, the Bu 3 Sn-mediated radical cyclization of enediynes exclusively forms the 5-exo-dig benzofulvene products. , …”

Section: Introductionmentioning

confidence: 99%

Alkenes as Alkyne Equivalents in Radical Cascades Terminated by Fragmentations: Overcoming Stereoelectronic Restrictions on Ring Expansions for the Preparation of Expanded Polyaromatics

et al. 2015

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Chemoselective interaction of aromatic enynes with Bu3Sn radicals can be harnessed for selective cascade transformations, yielding either Sn-substituted naphthalenes or Sn-indenes. Depending on the substitution at the alkene terminus, the initial regioselective 5-exo-trig cyclizations can be intercepted at the 5-exo stage via either hydrogen atom abstraction or C-S bond scission or allowed to proceed further to the formal 6-endo products via homoallylic ring expansion. Aromatization of the latter occurs via β-C-C bond scission, which is facilitated by 2c,3e through-bond interactions, a new stereoelectronic effect in radical chemistry. The combination of formal 6-endo-trig cyclization with stereoelectronically optimized fragmentation allows the use of alkenes as synthetic equivalents of alkynes and opens a convenient route to α-Sn-substituted naphthalenes, a unique launching platform for the preparation of extended polyaromatics.

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Section: Introductionmentioning

confidence: 99%

Alkenes as Alkyne Equivalents in Radical Cascades Terminated by Fragmentations: Overcoming Stereoelectronic Restrictions on Ring Expansions for the Preparation of Expanded Polyaromatics

et al. 2015

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“…While studying the reactivity of aryl-substituted arenediynes, we discovered that 1,2-bis(phenylethylnyl)benzene (PEB) forms a stable supercooled liquid at room temperature. Although PEB has been extensively studied to probe the Bergman cyclization reaction and to investigate its optical properties, ,− to the best of our knowledge, its crystal structure is not reported.…”

mentioning

confidence: 99%

“… Nonplanar molecules with limited conformational flexibility often lead to the formation of amorphous materials, and PEB falls into this category based on simulations with the B3LYP/6-31G(d) basis set (Figure S7). , Solution grown, diffraction quality crystals of PEB were attempted from common organic solvents such as cyclohexane, benzene, tetrahydrofuran, and chloroform at different temperatures (see Table S1). In spite of extensive experimentation with typical crystallization conditions, PEB generally remained in solution or oiled-out after solvent evaporation.…”

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confidence: 99%

Crystal Structure, Thermal Properties, and Shock-Wave-Induced Nucleation of 1,2-Bis(phenylethynyl)benzene

Ren

Lee

Hutchins

et al. 2016

Crystal Growth & Design

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We report the single crystal structure and thermal properties of 1,2-bis(phenylethynyl)benzene (PEB), revealing that PEB forms a metastable liquid at rt, ca. 35 °C below its melting point. Accelerated nucleation of PEB from its supercooled state was induced with high reproducibility by a shock wave with ca. 15 ns duration and 1.2 GPa peak pressure. By conducting shock wave experiments with varying peak pressures, we observed a correlation between the frequency of accelerated nucleation and shock intensity. The generality of shock-induced nucleation for supercooled liquids was probed with other organic supercooled liquids bearing phenyl rings. However, accelerated nucleation after shock wave impact was only observed for PEB, possibly due to the low rotational energy barrier of the terminal phenyl rings.

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Interplay between aromaticity and strain in double group transfer reactions to 1,2-benzyne

Fernández

Cossío

2016

J. Comput. Chem.

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Density Functional Theory calculations are used to explore the double hydrogen atom transfer from different alkanes to 1,2-benzyne. State-of-the-art calculations including the Activation Strain Model of reactivity, Energy Decomposition Analysis, and Valence Bond methods, reveal the origins of the relatively low activation barriers computed for these processes compared to the analogous reaction involving acetylene. In addition, the interplay between the in-plane aromaticity of the corresponding transition states and the variation of the π-aromaticity associated with the benzyne moiety as well as their influence on the barrier heights of the transformations are analyzed in detail.

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Synthesis and reactivity of anthracenyl-substituted arenediynes

Cited by 5 publications

References 26 publications

Alkenes as Alkyne Equivalents in Radical Cascades Terminated by Fragmentations: Overcoming Stereoelectronic Restrictions on Ring Expansions for the Preparation of Expanded Polyaromatics

Alkenes as Alkyne Equivalents in Radical Cascades Terminated by Fragmentations: Overcoming Stereoelectronic Restrictions on Ring Expansions for the Preparation of Expanded Polyaromatics

Crystal Structure, Thermal Properties, and Shock-Wave-Induced Nucleation of 1,2-Bis(phenylethynyl)benzene

Interplay between aromaticity and strain in double group transfer reactions to 1,2-benzyne

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