Study On The Synthesis Of Phosphates,Phosphonates,and Phospha-cyclopentanes By Lanthanide-Catalyzed Reactions

The lanthanide-catalyzed reactions for the synthesis of a-acylphosphates, y-oxophosphonates, and1,2-oxaphospholanes were studied in this thesis:1. An efficient method for the synthesis of a-acylphosphates by the lanthanide silylamides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3catalyzed reactions of diethyl phosphite with benzils was developed, which gave the corresponding products in moderate to high yields under mild conditions. The possible mechanism involving a phospha-aldol-Brook arrangement was proposed.2. Lanthanide aryloxides Ln(OAr)3(THF)2were found to be highly efficient catalysts for the selective phospha-Michael addition of diethyl phosphite to chalcones. y-Oxophosphonates were obtained as the only products in high yields under mild conditions. The possible mechanism of the reaction was proposed.3. Lanthanide silylamides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3were found to be efficient catalysts for the addition of diethyl phosphite to α,β-unsaturated ketones affording1,2-oxaphospholanes in moderate to high yields. The possible mechanism of the reaction was proposed.