The Study On Preparation And Reaction Performance Of Biphenyl Tertiary Phosphines With Carbon,Phosphorus And Axial Chirality

Chiral organophosphine ligands are of great significance in transition gold catalysis,and are widely used in asymmetric catalysis,organic synthesis and bioengineering.Phosphorus heterocycles have excellent steric structural stability and selectivity to other molecules,which have attracted people’s attention.Therefore,the synthesis of chiral P-heterocycles was launched.There are two main parts:The achiral CDOP is used as the starting material to prepare a seven-membered phosphorus heterocycles with phosphorus-axis chirality or a six-membered phosphorus heterocycles with carbon phosphorus axis chirality through a series of reactions;A seven-membered N-P heterocycles with carbon-phosphorus-axis chirality was prepared from o-aminobiphenyl as the starting material through a series of reactions.The first part:First,the biphenyl secondary phosphine compound 3 was synthesized by the method described in this article,and then reacted with aldehyde to produce a series of tertiary phosphine compounds 12 with a hydroxyl group at theα-position.Then,the intermediate product 13 is obtained by introducing chlorine into theα-position of compound 12 through Py/SOCl₂,and then intramolecular nucleophilic substitution occurs under alkaline conditions,and finally the cyclized tertiary phosphine compound 14 is obtained;LDA deprotonates theα-position of compound 14 to produce intermediate 16,which is then transformed into intermediate 17 by intramolecular rearrangement via the S_NAr,and finally 16 is obtained.The second part:we synthesized 6-chloro-5,6-dihydrodibenzazepine phosphine 20 by improving the previous method.After arylation and hydrolysis,nitrogen-containing secondary phosphine oxide 22 was obtained.At 60℃in THF to prepare a series of compounds 24,and exhibits a high yield and excellent selectivity.