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Theoretical study of stereoselectivity of the [1 + 2] cycloaddition reaction between (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6,4,0,01.3]dodec-9-ene and dibromocarbene using density functional theory (DFT) B3LYP/6-31G*(d)

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Abstract

In this work we used density functional theory (DFT) B3LYP/6-31G*(d) to study the stoichiometric reaction between the product (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6,4,0,01.3]dodec-9-ene (referred to here as P1) and dibromocarbene. We have shown that P1 behaves as a nucleophile, while dibromocarbene behaves as an electrophile; that the chemical potential of dibromocarbene is superior to that of P1 in absolute terms; and that P1 reacts with an equivalent quantity of dibromocarbene to produce two products: (1S,3R,8R,9S,11R)-10,10-dibromo-2,2-dichloro-3,7,7,11-tetramethyltetracyclo[6,5,0,01.3,09.11] tridecane (referred to here as P2) and (1S,3R,8R,9R,11S)-10,10-dibromo-2,2-dichloro-3,7,7,11-tetramethyltetracyclo[6,5,0,01.3,09.11] tridecane (referred to here as P3). P2 and P3 are formed at the α and β sides, respectively, of the C2 = C3 double bond of P1. This reaction is exothermic, stereoselective and chemospecific, and is controlled by charge transfer. Regioselectivity of the reaction was interpreted using the Lee-Yang-Parr functional.

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Authors and Affiliations

  1. Physical Chemistry Laboratory, Chemistry Department, Faculty of Science, Chouaïb Doukkali University, BP 20, 24000, El Jadida, Morocco

    Abdellah Zeroual & Abdeslam El Hajbi

  2. Biomolecular Chemistry Laboratory, Natural Substances and Reactivity, URAC 16, Semlalia Faculty of Science, Cadi Ayyad University, BP 2390, 40000, Marrakech, Morocco

    Ahmed Benharref

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  1. Abdellah Zeroual
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  2. Ahmed Benharref
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  3. Abdeslam El Hajbi
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Correspondence to Abdeslam El Hajbi.

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This paper belongs to Topical Collection QUITEL 2013

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Zeroual, A., Benharref, A. & El Hajbi, A. Theoretical study of stereoselectivity of the [1 + 2] cycloaddition reaction between (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6,4,0,01.3]dodec-9-ene and dibromocarbene using density functional theory (DFT) B3LYP/6-31G*(d). J Mol Model 21, 44 (2015). https://doi.org/10.1007/s00894-015-2594-4

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