Polymetallic oxygen cluster immobilized chiral catalyst, preparation method thereof and application thereof to chiral resolution and catalytic oxidation

Abstract

The invention discloses a polymetallic oxygen cluster immobilized chiral catalyst, a preparation method thereof and application thereof to chiral resolution and catalytic oxidation, belonging to the technical field of polymetallic oxygen cluster chiral catalysts. The preparation method mainly comprises the following three steps: synthesizing of hyamine type organic cations, the hydrophobic tail ends of which contain hydroxyl and chiral hydrophilic head groups; preparing a polymetallic oxygen cluster supramolecular complex with hydroxyl on t he periphery by carrying out electrostatic coating on a polymetallic oxygen cluster with the organic cations; preparing the chiral catalyst with the polymetallic oxygen cluster immobilized on silicon dioxide by carrying out hydrolyzation, polycondensation and hydroxyl exchange reaction on the supramolecular complex and a siloxane reagent. The polymetallic oxygen cluster supramolecular complex immobilization chiral catalyst can be used for the chiral resolution of racemic secondary alcohol substrates and the chiral catalytic reaction of sulfur ethers and olefin substrates. The method disclosed by the invention is commonly applicable to the polymetallic oxygen cluster with catalytic activity, simple in preparing and low in cost and the catalyst has important application value in the fields of chemical industry, medicines, materials and the like and can be recycled.

Description

technical field [0001] The invention belongs to the technical field of polymetallic oxygen cluster chiral catalysts, in particular to a method for covalently immobilizing polymetallic oxygen cluster chiral supramolecular complexes into silica through a sol-gel process and its application to chiral Splitting and catalytic oxidation reactions have important application value in chemical industry, medicine, materials and other fields. Background technique [0002] Polyoxometallic clusters, also known as polyoxometalates or polyacids, are a class of nanometer-sized inorganic clusters with defined chemical structures and compositions. Polyoxometallic clusters have a variety of structural forms and rich properties, showing great application potential in the fields of chemistry, materials, biology, and medicine. The important functional characteristics of polyoxometallic clusters have made the research on their catalysis very active (Pope M T, Müller A. Polyoxometalate chemistry: ...

AI Technical Summary

Problems solved by technology

However, the use of polymetallic oxygen clusters for chiral resolution and chiral catalytic oxidation has not been developed

Summarizing the results of literature and patents, we found that the chiral resolution reaction based on polymetallic oxygen clusters has not been systematically developed; The main factors of sexual selectivity are not clear enough; the recovery and reuse of polymetallic oxygen cluster chiral catalysts are not well resolved

It is very unfavorable for the further design of highly efficient polymetallic oxygen cluster chiral catalysts, and it is not conducive to the promotion of practical applications

[0004] In the core-shell structure of the polymetallic oxygen cluster supramolecular complex, it has been determined that organic cations can be bound to the anionic surface of the polymetallic oxygen cluster through electrostatic interactions, but the literature reports that organic cations have a mobile flow on the surface of the polymetallic oxygen cluster. Behavior, lateral movement along the surface can occur (Li H, Sun H, Qi W, Xu M, Wu L. Onionlike hybrid assemblies based on surfant-encapsulated polyoxometalates, Angew.Chem.Int.Ed.2007,46:1300– 1303), which greatly reduces the chiral selectivity of the substrate in the process of chiral resolution and chiral catalytic oxidation of polymetallic oxygen cluster chiral supramolecular complexes

Images