title: Inter- versus intra-molecular cyclization of tripeptides containing tetrahydrofuran amino acids: a density functional theory study on kinetic control.
abstract: Density functional B3LYP method was used to investigate the preference of intra- and inter-molecular cyclizations of linear tripeptides containing tetrahydrofuran amino acids. Two distinct model pathways were conceived for the cyclization reaction, and all possible transition states and intermediates were located. Analysis of the energetics indicate intermolecular cyclization being favored by both thermodynamic and kinetic control. Geometric and NBO analyses were performed to explain the trends obtained along both the reaction pathways. Conceptual density functional theory-based reactive indices also show that reaction pathways leading to intermolecular cyclization of the tripeptides are relatively more facile compared to intramolecular cyclization.
authors.affiliation: Center for Computational Natural Sciences and Bioinformatics, International Institute of Information Technology, Hyderabad 500 032, India.
authors.forename: N V Suresh
authors.initials: NV
authors.lastname: Kumar
authors.forename: U Deva
authors.initials: UD
authors.lastname: Priyakumar
authors.forename: Harjinder
authors.initials: H
authors.lastname: Singh
authors.forename: Saumya
authors.initials: S
authors.lastname: Roy
authors.forename: Tushar Kanti
authors.initials: TK
authors.lastname: Chakraborty
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D003500:Cyclization; D005663:Furans / Q000737:chemistry*; D006860:Hydrogen Bonding; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D009842:Oligopeptides / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000596:Amino Acids; D005663:Furans; D009842:Oligopeptides; C018674:tetrahydrofuran