Study On Transition-Metal-Catalyst-Free C–P Bond Construction

Organic phosphine compounds play an important role in organic chemistry,medicine,agricultural,materials.For example,phosphorus-containing compounds could be used as Wittig and Horner Wadsworth Emmons reagents,chiral ligands,enzyme inhibition agents,luminescent dyes and others.At present,the C–P bonds formation mainly involve traditional S_N2 reactions,cross-coupling methods,phosphorus radicals coupling to unsaturated bonds etc.However,there are still many challenges,Therefore,the development of transition-metal-free systems would be highly desirable and be attraction many scientisit.Based on previous work of our group,this paper mainly developed the base-enabled C–P bond construction using aryl alkyne compounds and aryl phosphine compounds as substrates.The sp~3 C–P bond and sp~2 C–P bond construct under mild conditions.This thesis will be including three chapters.The first chapter provided a review of the C–P bond construction:(1)methods of sp~3 C–P bond construction;(2)methods of sp~2 C–P bond construction;(3)methods of sp C–P bond construction.The second chapter mainly developed the transition-metal-free phosphine hydrogenation reaction of diarylacetylene and diaryloxyphosphorus to construct new sp~2 C–P bond under mild reaction conditions.This method with bifunctionalization and atom economy has high synthesis efficiency and practical application value.The third chapter mainly introduced the C≡C cleavage of acetylene compounds based on chapter two only by changing the solvent.This method provides a new methodology for the C≡C cleavage catalyzed by solvent and the synthesis of tertiary phosphines.