Theoretical insights into thermal cyclophanediene to dihydropyrene electrocyclic reactions; a comparative study of Woodward Hoffmann allowed and forbidden reactions

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• 作者：Bibi Saima ; Afsar Khan ; Riffat Un Nisa ; Tariq Mahmood…
• 关键词：Cyclophanediene ; Electrocyclization ; Allowed and forbidden reaction ; Density functional theory calculation
• 刊名：Journal of Molecular Modeling
• 出版年：2016
• 出版时间：April 2016
• 年：2016
• 卷：22
• 期：4
• 全文大小：1,297 KB
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• 作者单位：Bibi Saima (1)
  Afsar Khan (1)
  Riffat Un Nisa (1)
  Tariq Mahmood (1)
  Khurshid Ayub (1)
  
  1. Department of Chemistry, COMSATS Institute of Information Technology, University Road, Tobe Camp, Abbottabd, 22060, Pakistan
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Computer Applications in Chemistry
  Biomedicine
  Molecular Medicine
  Health Informatics and Administration
  Life Sciences
  Computer Application in Life Sciences
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：0948-5023

文摘

The thermally allowed electrocyclic reaction syn-cyclophanediene (CPD) to dihydropyrene (DHP) was compared with the disallowed thermal electrocyclic reaction in anti CPD through density functional theory (DFT) calculations at the B3LYP/6-31 + G(d) level. Moreover, the results were also compared with the electrocyclization of 1,3,5 hexatriene to 1,3-cyclohexadiene . The Woodward-Hoffmann (W-H) allowed thermal reaction in syn CPD 11 has a calculated activation barrier of 6.23 kcal mol−1, compared with 29 kcal mol−1 for the electrocyclization of 1,3,5 hexatriene to 1,3-cyclohexadiene. The enhanced acceleration of electrocyclization is believed to arise from geometrically enforced spatially aligned termini of the hexatriene. Substituents at the electrocyclic terminus of cyclophanediene significantly affected (up to three fold) the activation barriers. Mono-substitution of CPD has substituent dependent acceleration or deceleration whereas di-substitution always increased the activation barrier. The activation barrier for electrocyclization in 33 is 4.44 kcal mol−1, which is the lowest activation barrier for any thermal electrocyclic reaction. Cyclophanedienes (CPDs) substituted with electron-rich substituents cyclized with high activation barriers and vice versa, a phenomenon significantly different from electrocyclic reaction of 1,3,5-hexatriene where no such trend is traceable. Comparison of W-H allowed and forbidden electrocyclization in syn and anti CPDs, respectively, revealed quite similar electronic demand, although the transition states are different in nature. The transition state for a W-H forbidden reaction is biradicaloid, with most of the spin density at the electrocyclic termini; however, the transition state for a W-H allowed reaction has no such contribution. We also believe that this is the first study of its type, where W-H allowed and forbidden reactions are compared on a similar set of molecules, and compared for electronic effect through substituents.