5,5'-connected 1,1'-biphenyl axially chiral 2,2'-diphosphine ligand and preparation method thereof

Abstract

The invention relates to a 5,5'-connected 1,1'-biphenyl axially chiral 2,2'-diphosphine ligand and a preparation method thereof, and belongs to the technical field of chemical industry. The 5,5'-connected 1,1'-biphenyl axially chiral 2,2'-diphosphine ligand is a compound I with an (R) configuration and an (S) configuration axially or optically pure compounds II and III with (R) and (S) configurations axially. The preparation method comprises the following steps: converting substituted 4-metoxyphenol into a compound IV in an organic solution; converting the compound IV into a compound V; reacting the compound V with di(R<1>)phosphine oxyhydrogen to convert the compound V into a compound VI; converting the compound VI into a compound VII; reacting the compound VII with boron tribromide to prepare a compound VIII; reacting the compound VIII with dihalogenated hydrocarbon to prepare a 5,5'-connected compound IX with mixed (R) and (S) configurations, and performing splitting by chiral HPLC (High Performance Liquid Chromatography) to obtain compounds X and XI with single configuration of (R) and (S), thereby preparing the compound I or the compounds II and III. The 5,5'-connected 1,1'-biphenyl axially chiral 2,2'-diphosphine ligand can be synthesized into a catalyst by complexation with divalent metal of palladium, and high catalytic performance and high enantioselectivity can be obtained.

Description

[0001] This application is a divisional application of the following applications: filing date: September 2, 200; application number: 200910306495.X; invention title: "1,1'-biphenyl-like axial chirality 2 linked at 5,5' positions , 2'-bisphosphine ligand and its preparation method". technical field [0002] The invention relates to a compound in the technical field of chemical industry and a preparation method thereof, in particular to a 1,1'-biphenyl-like axial chiral 2,2'-bisphosphine ligand connected at the 5,5' position and its preparation method. Background technique [0003] The key to asymmetric catalytic synthesis is how to design and synthesize chiral catalysts with high selectivity and catalytic activity, in which chiral ligands are the source of asymmetric induction and control of catalysts. C 2 Due to its special structure, the type axial chiral bisphosphine ligands are widely used in metal-catalyzed asymmetric hydrogenation reactions, such as asymmetric cataly...

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Problems solved by technology

[0004] After searching the literature of the prior art, E.J.Corey et al published "The First Enantioselective Synthesis of the Chemotactic Factor Sirenin by an Intramolecular[2+1]Cyclization Using a New Chiral Catalyst" (a new type of chiral catalyst realized the enantioselective synthesis of Sirenin for the first time through the intramolecular [2+1] cyclization reaction), the chiral catalyst proposed in this paper The design concept of sexual ligands is to add two larger groups to the ortho-position of the biaryl axis to obtain stable axial chirality through their steric hindrance, but also limit the angle at which the biphenyl can rotate, that is Limits the size of the dihedral angle formed by the planes of the coupled biphenyl rings; and the size of the dihedral angle has been shown to affect the catalytic activity and selectivity of asymmetric catalytic reactions

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