title: Remarkably slow rotation about a single bond between an sp(3)-hybridised carbon atom and an aromatic ring without ortho substituents.
abstract: Look, no ortho substituents! A series of polycycles were prepared by using a three-component Joullié-Ugi reaction. The rate of rotation about the bond between a highly hindered bridgehead and a phenyl ring with no ortho substituents was measured, and was highly dependent on the substitution. Rotamer half-lives of up to 21 h at 298 K were observed (see figure). Rotamers resulting from this restricted rotation were isolated for the first time.A series of polycycles was prepared by using a three-component Joullié-Ugi reaction. The rate of rotation about the bond between a highly hindered bridgehead and a phenyl ring with no ortho substituents was measured by using, in general, variable-temperature HPLC. The rate of rotation was highly dependent on substitution and rotamer half-lives of up to 21 h at 298 K were observed. Insights into the effect of substitution on the rate of rotation were gleaned through electronic structure calculations on closely related derivatives. Rotamers resulting from restricted rotation about a bond between an sp(3)-hybridised carbon atom and a phenyl ring with no ortho substituents were isolated for the first time, and the equilibration of the separated rotamers was followed by using analytical HPLC. It was demonstrated, for the first time, that a highly hindered environment for the sp(3)-hybridised atom is sufficient for slow bond rotation about a single bond between sp(3)- and sp(2)-hybridised carbon atoms.
authors.affiliation: School of Chemistry, University of Leeds, UK.
authors.forename: Sarah
authors.initials: S
authors.lastname: Murrison
authors.forename: David
authors.initials: D
authors.lastname: Glowacki
authors.forename: Christian
authors.initials: C
authors.lastname: Einzinger
authors.forename: James
authors.initials: J
authors.lastname: Titchmarsh
authors.forename: Stephen
authors.initials: S
authors.lastname: Bartlett
authors.forename: Ben
authors.initials: B
authors.lastname: McKeever-Abbas
authors.forename: Stuart
authors.initials: S
authors.lastname: Warriner
authors.forename: Adam
authors.initials: A
authors.lastname: Nelson
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D004563:Electrochemistry; D015394:Molecular Structure; D011084:Polycyclic Aromatic Hydrocarbons / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; D002244:Carbon