The Woodward-Hoffmann-De Puy rule revisited

Organic Letters

Volumn 6, Issue 6, 2004, Pages 905-908

  Faza, Olalla Nieto ^a   López, Carlos Silva ^a   Álvarez, Rosana ^a   De Lera, Ángel R ^a  

^a UNIVERSITY OF VIGO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

BROMINE; CARBON; CYCLOPROPANE DERIVATIVE;

ARTICLE; CHEMICAL BOND; GAS; KINETICS; RING OPENING;

EID: 1642520269     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036449p     Document Type: Article

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29. A lower limit of 6.6 kcal/mol was estimated for the difference in activation energy between the two rotational directions available for the acetolysis of exo-7-tosyloxybicyclo[4.1.0]heptane at 150°C (ref 6c,d).
30. Transition structures for reactions cis-out and specially trans-in are more asynchronous. In both cases, the C-Br bond is almost entirely dissociated and the C-C bond distances are shorter than for the favored transition structures. Nevertheless, the activation energy for cis-out is lower than for trans-in, partly due to a residual interaction between the breaking C-C bond and the σ*(C-Br) orbital which is maintained in the less compact transition structure for the methyl rotating outward, and partly to the smaller steric hindrance to bond rotation. NBO analysis for trans-in reveals that the C-Br bond is fully dissociated and might better be described as an interaction of one empty orbital centered on carbon and another filled orbital on bromide. Although IRC analysis shows clearly that the computed transition structure connects reactants and products, TS-trans-in is similar to a cyclopropyl cation. All these features raise concerns on the consideration of the solvolytic ring-opening of trans,cis-1 by inward rotation of the methyl substituents as a concerted process. (18) Only inclusion of solvent allowed to locate the highly disfavored trans-in-7. This result indicates the destabilized nature of the forming carbenium ion in the trans-in-7 disrotation, particularly in the gas phase, due to the electron-withdrawing effect of the formyl group combined with the steric hindrance incured upon inward rotation.