A B3LYP study of the effects of phenyl substituents on 1,5-hydrogen shifts in 3-(Z)-1,3-pentadiene provides evidence against a chameleonic transition structure

Journal of the American Chemical Society

Volumn 126, Issue 32, 2004, Pages 10028-10034

  Hayase, Shuichi ^a,b   Hrovat, David A ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

^b TOTTORI UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL ACTIVATION; COMPUTATIONAL GEOMETRY; ENTHALPY; HYDROGEN;

ACTIVATION ENTHALPIES; ELECTRONIC COMPONENTS; TRANSITION STRUCTURE;

PHENOLS;

1,3 PENTADIENE DERIVATIVE; ALKADIENE; BENZENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; ENTHALPY; GEOMETRY; REACTION ANALYSIS; STRUCTURE ACTIVITY RELATION; SYNTHESIS;

EID: 4043179705     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja048708r     Document Type: Article

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44. Assuming that resonance structure C in Figure 5 represents the transfer of a hydrogen atom from C1 to C5 in the nodal plane of the allylic radical, Doering has used thermochemistry to estimate that this structure lies only a little more than 30 kcal/mol above the TS for a concerted 1,5-hydrogen shift in 1 and ca. 20 kcal/mol below the pentadienyl radical plus hydrogen atom in resonance structure A.26 B3LYP/6-31G* calculations give similar results, placing diradical C 27.7 kcal/mol above the TS and 20.1 kcal/mol below pentadienyl radical plus a hydrogen atom.
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