Compounds of chiral aromatic spiroketal diphosphine ligands, preparation methods and uses thereof

摘要

Disclosed are aromatic spiroketal diphosphine ligands, preparation methods and uses thereof. The ligands have the structure of formula (I), in which R1, R2, R3, R4, R5, R6, R7, R8, X and n are defined as such described in the specification. The aromatic spiroketal diphosphine ligands are prepared from aromatic spiroketal compounds. Also disclosed are the preparation methods of aromatic spiroketal compounds. The preparation methods are simple and can produce racemic or chiral aromatic spiroketal diphosphine ligands. The ligands can be used as catalysts of asymmetrical catalytic reactions having economical practicability and industry application prospect;

主权项

1. A preparation method for a compound of formula I, comprising a step of synthesizing the compound of formula I from a compound of formula II by reacting a compound of formula II with a reagent selected from the group consisting of R42PH, KPR42, LiPR42, KPR52, and LiPR52 , wherein R1, R2, R3, R6, R7 and R8 are each independently a hydrogen, a halogen, or a substituted or unsubstituted group selected from the group consisting of a C1-C10 alkyl, a C1-C4 alkoxyl, a C3-C30 cycloalkyl, and an aryl; R4 and R5 are each independently a substituted or unsubstituted group selected from the group consisting of C3-C10 cycloalkyl, a C1-C10 alkyl, 2-furyl, and an aryl; X is selected from the group consisting of CH2, NH, NCH3, O, and S; n=0-4; wherein a substituent for substitution is a halogen, a C1-6 alkyl, a C1-6 haloalkyl, or a C1-6 alkoxyl; Y is F, Cl, Br or I; and wherein when R4 and R5 are the same, the step of synthesizing the compound of formula I comprises reacting a compound of formula II with a reagent selected from the group consisting of R42PH, KPR42, and LiPR42, and when R4 and R5 are different, the step of synthesizing the compound of formula I comprises reacting a compound of formula II with a reagent selected from the group consisting of KPR42 and LiPR42, and then reacting with a reagent selected from the group consisting of KPR52 and LiPR52; provided that when the reagent is KPR42, LiPR42, KPR52, or LiPR42, then Y is F.