Portal de Periódicos da CAPES

The Effect of Carbonyl Substitution on the Strain Energy of Small Ring Compounds and Their Six-Member Ring Reference Compounds

2006; American Chemical Society; Volume: 128; Issue: 14 Linguagem: Inglês

10.1021/ja055086g

1943-2984

Robert D. Bach, Olga Dmitrenko,

Chemical Reaction Mechanisms

High level ab initio calculations have been applied to the estimation of ring strain energies (SE) of a series of three- and six-member ring compounds. The SE of cyclohexane has been estimated to be 2.2 kcal/mol at the CBS-APNO level of theory. The SE of cyclopropane has been increased to 28.6 kcal/mol after correction for the one-half of the SE of cyclohexane. The SEs of a series of carbonyl-containing three-member ring compounds have been estimated at the CBS-Q level by their combination with cyclopropane to produce a six-member ring reference compound. The SEs of cyclopropanone (5), the simplest α-lactone (6) [oxiranone], and α-lactam (7) [aziridinone] have been predicted to be 49, 47, and 55 kcal/mol, respectively, after correction for the SE of the corresponding six-member ring reference compound. The SEs of cyclohexanone, δ-valerolactone, and δ-valerolactam have been estimated to be 4.3, 11.3, and 5.1 kcal/mol, respectively. Marked increases in the SE of silacyclopropane and siladioxirane have been established, while significant decreases in the SEs of phosphorus, sulfur, dioxa- and diaza-containing three-member ring compounds were observed. The ring strain energies of the hydrocarbons (but not heterocycles) exhibit a strong correlation with their C−H bond dissociation energies.