Diels−Alder Cycloaddition of 11-Oxapentacyclo[6.5.2.23,6.02,7.09,13]- heptadeca-4,14,16-triene-4,5-dicarboxylic Anhydride with Cyclopentadiene and the Transannular Reactions of the Resulting Cycloadducts

Lin, Cheng‐Tung; Hsu, Hsiang-Chin; Chou, Teh‐Chang

doi:10.1021/jo990569m

Cited by 14 publications

(3 citation statements)

References 26 publications

(20 reference statements)

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“…The attack of an electrophile to a molecule having two isolated double bonds in spatial proximity usually leads to the transannular bridge formation in either cross (N-type) or parallel (U-type) manner or both. [1][2][3][4] Experimental results on this type of reaction have been confusing. In some cases, only the cross or the parallel bridged product is isolated, while in other cases both products are formed simultaneously.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, we aimed to study unique characteristics of these reactions, identify essential factors that determine the direction of reactions' flow and establish general rules that allow us to stipulate the factors that direct the flow of such reactions, and reaction products considering the results of this investigation and structure-characteristic relationships. In order to prove these suggested rules, electrophilic transannular addition reactions of bromine molecule to two face-to-face double bonded strained alkenes, namely tetracyclo[6.3.0 4,11 .0 5,9 ]undeca-2,6-diene(homohipostrofene) and endo,endo-tetracyclo[6.2.2.2 3,6 .0 2,7 ]tetradeca-4,9-diene(TCTD) were studied by DFT method.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons

Abbasoğlu

2017

ACSi

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Transannular electrophilic addition reaction of halogens to face-to-face(juxtaposed) double bonded strained alkenes were theoretically investigated. General rules that allow us to stipulate the factors that direct the main steps of the energy hypersurface of reactions as well as the products were established. Direction of the reaction flow is determined by direction of intramolecular skeletal isomerisation of cyclic-bridged halogenium cation and isomerisation takes place to create a more stable skeletal structure. Stability of resultant skeletal structure is determined by the number of σ bonds between isolated double bonds of the alkene and bonding-type of double bonds (N-and U-type). When the number of σ bonds between double bonds of the alkene is three (m = 3), the reaction takes place to predominantly give an N-type product, and when four (m = 4), N-and U-type products are formed. Structure and stability of cation intermediates (bridged, N-and U-type cations) of electrophilic addition reaction of homohipostrofen molecule, whose double bonds were linked by three σ bonds, with bromine were investigated by DFT methods in detail. Also the addition reaction of endo,endo-tetracyclo[6.2.2.2 3,6 .0 2,7 ]tetradeca-4,9-dien molecule, whose double bonds were linked by four σ bonds, with bromine were investigated by quantum chemistry.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons

Abbasoğlu

2017

ACSi

View full text Add to dashboard Cite

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“…Attack of an electrophile to a molecule having two isolated double bonds in spatial proximity usually leads to the transannular bridge formation in either cross (Ntype) or parallel (U-type) manner or both [6][7][8][9]. Experimental results on this type of reaction have been confusing.…”

Section: Introductionmentioning

confidence: 99%

DFT study on the electrophilic transannular addition reaction of bromine to tetracyclo[7.2.1.04,11.06,10]dodeca-2,7-diene

Abbasoğlu

Aşamaz

Магеррамов

et al. 2010

Journal of Molecular Structure: THEOCHEM

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Polytwistane

Barua

Quanz

Olbrich

et al. 2014

Chemistry A European J

129

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Twistane, C10H16, is a classic D2-symmetric chiral hydrocarbon that has been studied for decades due to its fascinating stereochemical and thermodynamic properties. Here we propose and analyze in detail the contiguous linear extension of twistane with ethano (ethane-1,2-diyl) bridges to create a new chiral, C2-symmetric hydrocarbon nanotube called polytwistane. Polytwistane, (CH)n, has the same molecular formula as polyacetylene but is composed purely of C(sp(3))-H units, all of which are chemically equivalent. The polytwistane nanotube has the smallest inner diameter (2.6 Å) of hydrocarbons considered to date. A rigorous topological analysis of idealized polytwistane and a C236H242 prototype optimized by B3LYP density functional theory reveals that the polymer has a nonrepeating, alternating σ-helix, with an irrational periodicity parameter and an instantaneous rise (or lead) angle near 15 °. A theoretical analysis utilizing homodesmotic equations and explicit computations as high as CCSD(T)/cc-pVQZ yields the enthalpies of formation Delta(f)H(0)°(twistane) = -1.7 kcal mol(-1) and Delta(f)H(0)°(polytwistane) = +1.28 kcal (mol CH)(-1), demonstrating that the hypothetical formation of polytwistane from acetylene is highly exothermic. Hence, polytwistane is synthetically viable both on thermodynamic grounds and also because no obvious pathways exist for its rearrangement to lower-lying isomers. The present analysis should facilitate the preparation and characterization of this new chiral hydrocarbon nanotube.

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Diels−Alder Cycloaddition of 11-Oxapentacyclo[6.5.2.2^3,6.0^2,7.0^9,13]- heptadeca-4,14,16-triene-4,5-dicarboxylic Anhydride with Cyclopentadiene and the Transannular Reactions of the Resulting Cycloadducts

Cited by 14 publications

References 26 publications

Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons

Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons

DFT study on the electrophilic transannular addition reaction of bromine to tetracyclo[7.2.1.04,11.06,10]dodeca-2,7-diene

Polytwistane

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