Transition structure for the retroene-type elimination reaction of propene from allylamines

Rodríguez, Leonardo Jiménez; Muoz, Wasdin; Martín, Gonzalo; Ocando-Mavárez, Edgar

doi:10.1002/(sici)1098-1071(1997)8:1<85::aid-hc14>3.0.co;2-0

Cited by 4 publications

References 22 publications

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Retro‐Ene Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The intramolecular thermolysis of organic compounds with an unsaturated functional group involving the transfer of a γ‐hydrogen to the unsaturated center via a six‐membered transition state to yield both ene and enophil is generally known as the retro ‐ene reaction or retro ‐ene fragmentation. The study finds that in most cases, this reaction involves a concerted mechanism, and gives a product with the stereochemical integrity preserved. This reaction does not take place among cyclic alkenes smaller than a seven‐membered ring or fused rings except for a cyclopropyl ring. This reaction has broad applications in organic synthesis.

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Retro‐Ene Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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Transition‐state geometry and activation energy calculation for the retro‐ene elimination reaction of propene from diallyl sulfide

Rodríguez¹,

Fermín²,

Áñez³

et al. 2002

J of Physical Organic Chem

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The transition‐state geometry and the activation energy for the retro‐ene elimination of propene from diallyl sulfide were calculated at three levels of ab initio molecular orbital theory [HF, DFT(B3LYP) and MP2] combined with three basis sets (3–21G*, 6–31G* and 6–31 + G**). The activation energies were determined at room temperature and at 375 °C and compared with experimental data. Our calculations lead to transition states that consist of a non‐planar six‐center cyclic structure with a distorted chair‐like geometry. Moreover, the transition‐state geometry has a marked ‘product‐like’ character. We found that the B3LYP/6–31G* level produce activation values closer to the experimental values in a reasonable time. In all cases studied, the activation energies obtained from both the density functional and MP2 are better than those obtained using the Hartree–Fock method, which overestimates the barrier height. Regardless of the level of theory used [HF, DFT(B3LYP) or MP2], the basis sets 6–31G* and 6–31 + G** produce practically the same values of the activation energy; however, the first set is about twice as fast as the second. The transition‐state geometry obtained by different levels showed only slight structural differences. Copyright © 2002 John Wiley & Sons, Ltd.

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