Mechanism of 1,3-migration in allylperoxyl radicals: Computational evidence for the formation of a loosely bound radical - dioxygen complex

Journal of the American Chemical Society

Volumn 125, Issue 35, 2003, Pages 10641-10650

  Olivella, Santiago ^a   Solé, Albert ^b  

^a CSIC   (Spain)

^b UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

BIOCHEMISTRY; CHARGE TRANSFER; CHEMICAL BONDS; COMPLEXATION; DISSOCIATION; ELECTRONIC STRUCTURE; LIPIDS; MOLECULAR VIBRATIONS; OXIDATION; PHASE TRANSITIONS; QUANTUM THEORY; REACTION KINETICS; STEREOCHEMISTRY;

REARRANGEMENT REACTIONS;

FREE RADICALS;

LOW DENSITY LIPOPROTEIN; OXYGEN; PEROXY RADICAL;

AGING; ARTICLE; AUTOOXIDATION; COMPLEX FORMATION; ELECTRON TRANSPORT; ENZYME MECHANISM; PHASE TRANSITION; PROTEIN DNA INTERACTION; PROTEIN MODIFICATION; QUANTUM MECHANICS; RING OPENING; STRUCTURE ANALYSIS;

EID: 84961978407     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja030171e     Document Type: Article

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64. In relation to the interpretation of the experiments that describe the stereochemical transfer of chiriality in the allylperoxyl rearrangement, an anonymous referee has raised the question of whether calculations on the difference in energy of the complex CX having a methyl substituent on C1 in the two possible orientations (i.e., pseudo trans and pseudo cis to the C2-C3 bond) would explain the overall stereochemical outcome. To investigate this interesting point, we have carried out preliminary calculations on the relative energies of the pseudo trans and pseudo cis methyl substituted complex CX. At the UMP2 level of theory with the 6-311+G-(2df.p) basis set, including the ZPVE correction, the pseudo trans conformation turns out to be 0.5 kcal/mol less energetic than the pseudo cis one. This results account for two important experimental facts (ref 12b): (1) while the allylperoxyl rearrangement is highly stereoselective. the rearrangements starting from an allylperoxyl radical having a cis substituent in the double bond occur with les stereoselectivity than rearrangements proceeding from an allylperoxyl radical having a trans substituent, and (2) rearrangements across a trans double bond occur more readily than rearrangements across a cis double bond. Following another interesting suggestion by the same anonymous referee, we have carried out additional calculations on the relative energies of the complex CX having a methyl substituent on both C1 and C3 in the three possible orientations (i.e., trans-trans, trans-cis, and cis-cis). At the UMP2/6-311+G(2df,p) plus ZPVE correction, the relative energies of these structures are found to be 0.0. 0.5, and 3.7 kcal/mol, respectively. Therefore, these results nicely agree with the aforementioned experimental findings.