Studies On Transition-Metal-Catalyzed Carbon–Phosphorus Bond Construction

The organophosphorus compounds are widely used in organic synthetic chemistry and life science by virtue of their unique bioactivities and inherent chemical properties.Therefore,the development of succinct and efficient strategies to construct carbon–phosphorus bond has been the focus of attention.The transition-metal-catalyzed carbon-phosphorus construction via direct carbon-hydrogen bond functionalization is the most atom economy and environment-friendly strategy.This paper not only presents an overview of recent evolutions in transition-metal-catalyzed carbon-phosphorus construction,but also introduces four methods of transition-metal-catalyzed carbon-phosphorus construction in detail.The thesis contains five parts as follows:1.The development of new strategies to construct Carbon–Phosphorus bond were classified and analyzed,The main contents include the brief introduction of the new strategy to construct Carbon–Phosphorus bond in recent years2.We developed a novel and convenient Rh-/Ni-catalyzed cascade sequence of allylamine isomerization/hydrophosphonylation for the synthesis of various ?-Aminophosphonates.Based on the experimental studies of the mechanism,we proposed the catalytic process of allylamine isomerisation to enamine intermediate which underwent through the ?-allyl mechanism.3.We presented a facile and efficient method of silver-catalyzed phosphonylation of unprotected propargylic alcohols with P(O)H compounds to the synthesis of allenylphosphoryl compounds.This transformation could be conducted under mild reaction conditions without ligand,base,and additive.Moreover,the reaction pathway may involve in a MeyerSchuster rearrangement and the only byproduct is water.4.We introduced a copper-catalyzed alkene oxidative cross-coupling reaction with various H-P(O)compounds in detail.The copper salts and oxidants control the regioselectivity and stereoselectivity of the reaction.Based on the study of preliminary mechanism,we proposed the mechanism of free radical.5.We descried a silver-catalyzed cascade radical cyclization for stereoselective synthesis of exocyclic phosphine oxides.The reaction exhibits high regioselectivity and stereoselectivity.