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<p>DFT study of the mechanism and stereochemistry of electrophilic transannular addition reaction of bromine to 6-oxa-heptacyclo[9.6.2.2<sup>3,9</sup>.1<sup>13,16</sup>.0<sup>2,10</sup>.0<sup>4,8</sup>.0<sup>12,17</sup>]docosan-14,18,20-triene-12,17-dicarboxylic anhydride</p><p style="text-align: justify;"> </p>

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Title Statement <p>DFT study of the mechanism and stereochemistry of electrophilic transannular addition reaction of bromine to 6-oxa-heptacyclo[9.6.2.2<sup>3,9</sup>.1<sup>13,16</sup>.0<sup>2,10</sup>.0<sup>4,8</sup>.0<sup>12,17</sup>]docosan-14,18,20-triene-12,17-dicarboxylic anhydride</p><p style="text-align: justify;"> </p>
 
Added Entry - Uncontrolled Name Abbasoglu, Rza ; Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey
Atalay, Abdurrahman ; Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey
 
Uncontrolled Index Term theoretical and quantum chemistry
Theoretical chemistry, Density functional calculations, Electrophilic transannular addition, Transannular addition,Juxtaposed double bonds, Intramolecular skeletal rearrangement
 
Summary, etc. <p>The geometry and the electronic structure of 6-oxa-heptacyclo[9.6.2.2<sup>3,9</sup>.1<sup>13,16</sup>.0<sup>2,10</sup>.0<sup>4,8</sup>.0<sup>12,17</sup>] docosan-14,18,20-triene-12,17-dicarboxylic anhydride (HDTD) have been investigated by DFT methods. The study shows that the norborneyl double bond of the HDTD molecule is endo pyramidalized and the central and bicyclo[2,2,2]octenyl double bonds are exo pyramidalized. The structure and stability of the cation intermediates and products of the reaction have been investigated by DFT methods. The most stable cation intermediate is U-N-type ion and the reaction takes place over this cation. The cation centre of U-N-type ion mutually interacts with the unshared electron pair of the oxygen atom of the tetrahydrofuran ring on the exo face and is sterically hindered by the tetrahydrofuran ring. The nucleophilic attack of bromide anion (Br<sup>–</sup>) on the cation centre of U-N-type ion occurs on the endo face and as a result the exo,endo-dibromide isomer of U-N-type product is obtained, which is 6.913 kcal mol<sup>-1 </sup>more stable than the exo,exo-isomer.</p><p style="text-align: justify;"> </p>
 
Publication, Distribution, Etc. Indian Journal of Chemistry -Section A (IJCA)
2020-12-10 11:43:03
 
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http://op.niscair.res.in/index.php/IJCA/article/view/12172
 
Data Source Entry Indian Journal of Chemistry -Section A (IJCA); ##issue.vol## 56, ##issue.no## 8 (2017): INDIAN JOURNAL OF CHEMISTRY - SECTION A
 
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Nonspecific Relationship Entry http://op.niscair.res.in/index.php/IJCA/article/download/12172/34752
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34753
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34754
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34755
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34756
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34757
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34758
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34759
http://op.niscair.res.in/index.php/IJCA/article/download/12172/34760
 
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