Synthesis, optical resolution, and configurational assignment of novel axially chiral quateraryls.
A one-pot general synthesis of highly functionalized quateraryls through carbanion-induced, base-catalyzed ring transformation of 5,6-diaryl-2H-pyran-2-ones and core-substituted phenylacetones is delineated. These conversions were found to give diversely functionalized benzenes bearing peripheral aryl rings, some of which possess inherent atropisomerism. Exemplarily for one of the quateraryls, the optical resolution of the respective atropo-enantiomers by HPLC on a chiral phase and the assignment of their absolute axial configurations succeeded by LC-CD coupling in combination with semiempirical CNDO/S and TDDFT CD calculations. This synthetic approach offers-in a transition metal-free environment-high flexibility in the construction of quateraryls with the desired conformational freedom along the molecular axis, which may help in exploring and developing new potential ligands for asymmetric synthesis.
Goel
Atul
A
Division of Medicinal and Process Chemistry, Central Drug Research Institute, Lucknow 226001, India. agoel13@yahoo.com
Singh
Fateh V
FV
Kumar
Vijay
V
Reichert
Matthias
M
Gulder
Tobias A M
TA
Bringmann
Gerhard
G
D001713:Biphenyl Compounds / Q000138:chemical synthesis / Q000737:chemistry; D002942:Circular Dichroism; D008968:Molecular Conformation; D013237:Stereoisomerism; D013730:Terphenyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*