title: Control of conformer population and product selectivity and stereoselectivity in competitive photocyclization/rearrangement of chiral donor-acceptor dyad.
abstract: The conformer population and the relative excitation efficiency of each conformer, assessed by theoretical and experimental examinations, enabled us to precisely control the chemo- and diastereoselectivities of the competitive photocyclization/rearrangement reaction of a chiral donor-acceptor (D/A) dyad by irradiation wavelength, solvent polarity, and reaction temperature. Manipulating the ground- and excited-state conformer equilibria is essential for critically controlling the intramolecular D/A system, in sharp contrast to the rather divergent excited species involved in relevant intermolecular systems.
authors.affiliation: Department of Applied Chemistry, Osaka University, 2-1 Yamada-oka, Suita 565-0871, Japan.
authors.forename: Emi
authors.initials: E
authors.lastname: Nishiuchi
authors.forename: Tadashi
authors.initials: T
authors.lastname: Mori
authors.forename: Yoshihisa
authors.initials: Y
authors.lastname: Inoue
mesh_terms: D000475:Alkenes / Q000737:chemistry; D001667:Binding, Competitive; D003500:Cyclization; D008958:Models, Molecular; D008968:Molecular Conformation; D055668:Photochemical Processes; D013237:Stereoisomerism; D013379:Substrate Specificity; D013696:Temperature
chemical_list: D000475:Alkenes