title: The nature of persistent conformational chirality, racemization mechanisms, and predictions in diarylether heptanoid cyclophane natural products.
abstract: Restricted rotations of chemical bonds can lead to the presence of persistent conformational chirality in molecules lacking stereocenters. We report the development of first-of-a-kind predictive rules that enable identification of conformational chirality and prediction of racemization barriers in the diarylether heptanoid (DAEH) natural products that do not possess stereocenters. These empirical rules-of-thumb are based on quantum mechanical computations (SCS-MP2/∞//B3LYP/6-31G*/PCM) of racemization barriers of four representative DAEHs. Specifically, the local symmetry of ring B and the E/Z configuration of the vinylogous acid/ester are critical in determining conformational chirality in the DAEH natural product family.
authors.affiliation: Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331-4003, USA. paulc@science.oregonstate.edu christopher.beaudry@oregonstate.edu.
authors.forename: Ommidala
authors.initials: O
authors.lastname: Pattawong
authors.forename: M Quamar
authors.initials: MQ
authors.lastname: Salih
authors.forename: Nicholas T
authors.initials: NT
authors.lastname: Rosson
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Beaudry
authors.forename: Paul Ha-Yeon
authors.initials: PH
authors.lastname: Cheong
mesh_terms: D001688:Biological Products / Q000737:chemistry*; D036381:Diarylheptanoids / Q000737:chemistry; D004988:Ethers, Cyclic / Q000737:chemistry*; D006860:Hydrogen Bonding; D007700:Kinetics; D008968:Molecular Conformation; D013237:Stereoisomerism; D013816:Thermodynamics; D000097566:Cyclophanes
chemical_list: D001688:Biological Products; D036381:Diarylheptanoids; D004988:Ethers, Cyclic; C583505:garugamblin; D000097566:Cyclophanes