title: Conformational preferences of cis-1,3-cyclopentanedicarboxylic acid and its salts by 1H NMR spectroscopy: energetics of intramolecular hydrogen bonds in DMSO.
abstract: The conformational populations of cis-1,3-cyclopentanedicarboxylic acid (1) and its mono- and dianion were established in DMSO solution by comparing the vicinal proton–proton coupling constants (3J(HH)) obtained in solution to their theoretical counterparts. Geometries used for 3J(HH) theoretical estimation (using Karplus-type equations) were obtained from optimized structures at the B3LYP/6-31G(2d,2p) level. The diacid (1) adopted many conformations, whereas the ionized species (1A mono- and 1B dianion) assumed single conformations. A downfield chemical shift of 19.45 ppm (Δδ(H) = 7.43 ppm) observed at −60 °C was indicative of intramolecular hydrogen bonding in 1A, which was later corroborated by determining the ratio of the first (K1) to the second (K2) ionization constants. K1/K2 in DMSO (1.3 × 10(7)) was significantly larger than the value in water (2 × 10). In addition, K1/K(E) = 200 (where K(E) is the acidity constant of the monomethylester of 1) was greater than the intramolecular hydrogen bonding threshold value of 2. The calculated intramolecular hydrogen bond strength of 1A was ~3.1 kcal mol(–1), which is ~2.7 kcal mol(–1) more stable than the values for cis-1,3-cyclohexanedicarboxylic acid (2A). Thus, the relative energies of intramolecular hydrogen bonding in the monoanions 1A and 2A suggests that 1,3-diaxial conformers are more favored for cyclopentane than for cyclohexane rings.
authors.affiliation: Gates and Crellin Laboratories of Chemistry, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: Bright U
authors.initials: BU
authors.lastname: Emenike
authors.forename: William R
authors.initials: WR
authors.lastname: Carroll
authors.forename: John D
authors.initials: JD
authors.lastname: Roberts
mesh_terms: D003510:Cyclohexanes / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: D003510:Cyclohexanes; D003517:Cyclopentanes; C582143:cis-1,3-cyclopentanedicarboxylic acid; D004121:Dimethyl Sulfoxide