Three-carbon dowd-beckwith ring expansion reaction versus intramolecular 1,5-hydrogen transfer reaction: A theoretical study

Journal of Organic Chemistry

Volumn 70, Issue 23, 2005, Pages 9417-9423

  Ardura, Diego ^a   Sordo, Tomás L ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; BENZENE; CONFORMATIONS; HYDROGEN; MASS TRANSFER; MOLECULAR STRUCTURE; STRUCTURE (COMPOSITION);

DOWD-BECKWITH RING EXPANSION; PRIMARY RADICALS;

AROMATIC COMPOUNDS;

BENZENE; CARBON; CARBOXYLIC ACID DERIVATIVE; CYCLOOCTANE DERIVATIVE; HYDROGEN; METHYL 1 (3 IODOPROPYL) 2 METHYL 5 OXOCYCLOPENTANECARBOXYLATE; RADICAL; SOLVENT; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATION; DOWD BECKWITH RING EXPANSION REACTION; ENERGY; MOLECULAR STABILITY; PROTON TRANSPORT; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; THEORY;

EID: 27744504886     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo051551g     Document Type: Article

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21. To benchmark the theory level employed in the present work we performed geometry optimization of the reactant, the rate-determining TSs, TS1E and TS2T, and PE and PT products for the ring expansion and 1,5-H transposition in the primary radical from 1-(3-iodopropyl)-2-oxocyclopentanecarboxylate, 16, at the UBHandHLYP/6-31G(d,p) theory level, and single-point ROMP2/6-311++G(2d,2p)// UBHandHLYP/6-31G(d,p) calculations. We found that, in general, bond lengths are slightly larger with the UBHandHLYP functional (the mean difference is about 0.01 Å). The ROMP2/6-311++G(2d,2p)//UBHandHLYP/6-31G(d,p) Gibbs energy barriers in solution are 11.7 kcal/mol for TS1E and 12.5 kcal/mol for TS2T. The reaction energies are -9.9 kcal/mol for the ring expansion and -0.9 kcal/mol for the 1,5-H transposition. Thus, the energy barriers obtained with the UBHandHLYP functional differ from those obtained with the B3LYP one only by 0.1-0.2 kcal/mol, whereas the largest difference was found for the reaction energy for the transposition (1.1 kcal/mol). Therefore, the ROMP2/6-311++G(2d,2p)//UB3LYP/ 6-31G(d,p) theory level used in this work seems to be adequate for the present study. The geometries and energies obtained in this benchmarking can be found in Figure 5S and Table 6S of the Supporting Information.