Synthesis of Chiral Vanadium Phosphonates and Their Catalytic Activity
Treatment of vanadium starting materials with chiral and achiral phosphonic acids and phosphonates provided the soluble [BuPPh3]4[(V 2O2(OH)2)6(O3PR)8] R = CH(CH2Ph)Pr and CH(Et)Pr, [(VO)6(O3PR) 8{Cl}] R = CH2Ph, CHMePh-S, and [(V 14O22)(OH)4(O3PR)8] 6- with R = CHEtPr, CH(CH2Ph)Pr, and CH(Me)Ph- S cage complexes. These are the first reported examples of vanadium phosphonate cage molecules synthesized with racemic and enantiopure phosphonate starting materials. In addition, treatment of V2O 5 with (HO)2P(O)R in ethanol, where R = Ph and CHMePh- S, afforded (VO)(O3PR)·yEtOH·xH2O. (VO)(O3PCHMePh-S)·H2O is the first layered vanadium phosphonate material synthesized using an enantiopure phosphonic acid. These materials were tested for catalytic activity in the asymmetric epoxidation of geraniol and cinnamyl alcohol.
University of Illinois - Urbana-Champaign
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University of Illinois at Urbana-Champaign