title: Synthesis of 11-cis-locked bicyclo[5.1.0]octanyl retinal and an enantioselective binding to bovine opsin.
abstract: Both enantiomers of 13-(E) and 13-(Z) isomers of 11-cis-locked bicyclo[5.1.0]octanyl retinal were prepared by an improved synthesis and incubated with bovine opsin. The synthesis also establishes the absolute configuration of the enantiomers. Only one of the enantiomers binds to opsin, thus showing the steric restrictions regarding the middle polyene moiety of the retinoid molecule; this is in sharp contrast to the known leniency of the ring moiety binding site of retinoids. However, although one enantiomer is incorporated into the pigment, the circular dichroic spectrum of the pigment incorporating the bound enantiomer yields only a very weak Cotton effect, showing that, once incorporated, the bicyclo[5.1.0]octanyl chromophore is flattened by the opsin binding site. The titled retinoid was synthesized for study of the absolute conformation of the retinal pigment in rhodopsin.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: Yukari
authors.initials: Y
authors.lastname: Fujimoto
authors.forename: Rongyuan
authors.initials: R
authors.lastname: Xie
authors.forename: Sarah E
authors.initials: SE
authors.lastname: Tully
authors.forename: Nina
authors.initials: N
authors.lastname: Berova
authors.forename: Koji
authors.initials: K
authors.lastname: Nakanishi
mesh_terms: D000818:Animals; D001665:Binding Sites; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D002417:Cattle; D002942:Circular Dichroism; D066298:In Vitro Techniques; D009682:Magnetic Resonance Spectroscopy; D012172:Retinaldehyde / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D017299:Rod Opsins / Q000378:metabolism*; D013237:Stereoisomerism
chemical_list: D001643:Bridged Bicyclo Compounds; D017299:Rod Opsins; D012172:Retinaldehyde