Studies on the enantioselective catalysis of photochemically promoted transformations: "sensitizing receptors" as chiral catalysts.
A strategy for the enantioselective catalysis of photomediated reactions in solution is described, involving the use of chiral molecular receptors possessing appendant triplet-sensitizing moieties. Energy transfer is selectively directed to bound substrate as a consequence of the distance dependence of triplet-triplet energy transfer. This effect, which is equivalent to a binding-induced rate enhancement, enables substoichiometric chirality transfer from the receptor template to the substrate, as observed in the intramolecular enone-olefin photo[2 + 2]cycloaddition of a quinolone substrate.
Cauble
David F
DF
Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
Lynch
Vincent
V
Krische
Michael J
MJ
D001577:Benzophenones / Q000138:chemical synthesis*; D001665:Binding Sites; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010777:Photochemistry; D015363:Quinolones / Q000737:chemistry; D013237:Stereoisomerism
D001577:Benzophenones; D006571:Heterocyclic Compounds; D008024:Ligands; D015363:Quinolones