Study On The Application Of Mesoporous Materials In Catalyzing The Reaction Of C-P Bonds Construction And Supporting P-Chiral Molecules

In this paper,we mainly study the synthesis of phosphine oxide compounds catalyzed by mesoporous graphite carbon nitride(mpg-CN)induced by visible light and explored the asymmetric catalytic synthesis of P-chiral organic phosphine compounds and load these phosphine chiral molecules onto mesoporous materials.In the first part,we developed the visible light induced mpg-CN-Ni-dual-catalytic C(sp2)-C(sp3)Cross-Coupling Reactions.These reactions used diarylphosphine oxides or phosphite esters as substrates to react with aryl bromides.The reaction conditions were optimized.A series of tertiary arylphosphine oxides and tertiary arylphosphine esters were obtained with a high yield(76-99%).The reaction could occur in both aryl bromides with electron-drawing groups and electron-donating groups.There is also a good tolerance to heteraryl bromide,including 3-pyridinyl,6-indolyl and 7-quinolinyl.In the second part,we developed the visible light induced the region and stereoselective addition of diarylphosphine oxide to alkynes using mesoporous graphite carbon nitride(mpgCN)as photoredox catalyst.With condition optimization,A series of Z-alkenylphosphine oxides were obtained with medium yield(37-86%).The method used water as solvent and no transition metal was involved.Z-alkenylphosphine oxides can be regionally and stereoselectively obtained for both electron-rich and electron-deficient aryl acetylenes,This method is also suitable for non-terminal alkynes.In the third part,the asymmetric Michael addition of phenylphosphine to phenylazo compounds was achieved by the pincer nickel complex,and some P-chiral secondary phosphine compounds were obtained with 63-97%yield and up to 95%ee.The follow-up alkylation upon P-H bond with alkyl halides and nucleophilic substitution upon P-N bond with alcohols can be occurred sequentially and stereospecifically to access P-chiral compoun-ds with diverse functional groups.Finally,the chiral molecules of phosphine were loaded onto the mesoporous material SBA-15 by this method.