Developing a new class of axial chiral phosphorus ligands: preparation and characterization of enantiopure atropisomeric phosphinines.
Both enantiomers of the first atropisomeric phosphinine (1) have been isolated by using analytical HPLC on a chiral stationary phase. The enrichment of one enantiomer and a subsequent investigation into its racemization kinetics revealed a barrier for internal rotation of DeltaG(298)(double dagger) = (109.5+/-0.5) kJ mol(-1), which is in excellent agreement with the theoretically predicted value of DeltaG(298)(double dagger) =116 kJ mol(-1). Further analysis with UV and circular dichroism spectroscopies and density functional theory calculations led to the determination and assignment of the absolute configurations of both enantiomers. These results are the basis for future investigations into this new class of axially chiral phosphinine-based ligands and their possible applications in asymmetric homogeneous catalysis.
Müller
Christian
C
Department of Chemical Engineering and Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands. c.mueller@tue.nl
Pidko
Evgeny A
EA
Staring
Antonius J P M
AJ
Lutz
Martin
M
Spek
Anthony L
AL
van Santen
Rutger A
RA
Vogt
Dieter
D
D001555:Benzene Derivatives / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007700:Kinetics; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D013237:Stereoisomerism
D001555:Benzene Derivatives; D008024:Ligands; D009943:Organophosphorus Compounds; C519090:phosphinine; D010758:Phosphorus