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CN-122006814-A - Preparation method of Taniaphos-supported catalyst by solvent weaving method

CN122006814ACN 122006814 ACN122006814 ACN 122006814ACN-122006814-A

Abstract

The invention discloses a preparation method of a solvent braiding method supported Taniaphos catalyst, and belongs to the technical field of organic chemistry. The method comprises the steps of adding a taniahos ligand and metal salt into a reaction container at room temperature, adding a solvent under the atmosphere of inert gas, stirring at room temperature until the mixture is completely dissolved, adding an aryl-containing comonomer to obtain a reaction solution, adding Lewis acid or Bronsted acid, and carrying out a Friedel-crafts alkylation reaction to obtain a supported taniahos catalyst, wherein the aryl-containing comonomer comprises at least one of biphenyl, triphenylbenzene, diphenylmethane, triphenylmethane, furan, thiophene and pyrrole. The method is simple and efficient, the supported Taniaphos catalyst shows excellent catalytic activity and good stability in asymmetric allylation reaction of cinnamyl bromide substrate, and the product is obtained only by distillation after solvent extraction without column chromatography. The catalyst activity remains unchanged after the catalyst is recycled for 5 times.

Inventors

  • YOU HENGZHI
  • WANG CHAO
  • WU LIPING
  • Liao Jingyuan
  • HUANG JUNRONG
  • ZHU YUXIANG
  • CHEN FENER

Assignees

  • 深圳连续制药科技有限公司

Dates

Publication Date
20260512
Application Date
20251210
Priority Date
20250815

Claims (10)

  1. 1. The preparation method of the supported taniahos catalyst is characterized by comprising the following steps of adding a taniahos ligand and metal salt into a reaction container at room temperature, adding a solvent in an inert gas atmosphere, stirring at room temperature until the mixture is completely dissolved, adding an aryl-containing comonomer, and continuously stirring and dissolving to obtain a reaction solution; adding Lewis acid or Bronsted acid into the reaction liquid to carry out a Friedel-crafts alkylation reaction to obtain a supported Taniaphos catalyst; Wherein the comonomer containing aryl comprises at least one of biphenyl, triphenylbenzene, diphenylmethane, triphenylmethane, furan, thiophene and pyrrole.
  2. 2. The production method according to claim 1, wherein the metal salt comprises at least one of cuprous bromide dimethyl sulfide, cuprous chloride, thiophene cuprous diformate, tetra acetonitrile copper tetrafluoroborate, tetra acetonitrile copper hexafluorophosphate, bis (dicyclopentadiene) rhodium tetrafluoroborate, 1, 5-cyclooctadiene rhodium chloride dimer, 1, 5-cyclooctadiene iridium chloride dimer, and/or the addition amount of the metal salt is 0.5 to 1 equivalent with respect to Taniaphos ligand.
  3. 3. The method according to claim 1, wherein the solvent comprises at least one of dichloromethane, chloroform, carbon tetrachloride, dimethoxymethane, trimethoxymethane, and dichloroethane, and/or the solvent is added so that the concentration of Taniaphos ligand is 0.02-1 mmol/ml, and/or the solvent is added, and stirring is continued for 15-60 minutes after stirring at room temperature until complete dissolution.
  4. 4. The process according to claim 1, wherein the aryl group-containing comonomer is added in an amount of 1 to 75 equivalents relative to the Taniaphos ligand.
  5. 5. The process according to claim 1, wherein the Lewis acid comprises at least one of ferric chloride, aluminum trichloride and stannic chloride, and/or the Bronsted acid comprises at least one of concentrated sulfuric acid and trifluoromethanesulfonic acid, and/or the Lewis acid or Bronsted acid is used in an amount of 5 to 75 equivalents relative to the Taniaphos ligand, and/or the addition of the Lewis acid or Bronsted acid is carried out under an inert gas flow.
  6. 6. The method according to claim 1, wherein the reaction vessel is closed after adding a lewis acid or a bronsted acid to the reaction solution.
  7. 7. The preparation method according to claim 1, wherein the reaction time of the friedel-crafts alkylation reaction is 1-48 h, and the reaction is quenched by a quencher, wherein the quencher comprises at least one of absolute ethanol, absolute methanol and aqueous hydrochloric acid; And/or the reaction temperature of the Friedel-crafts alkylation reaction is-20 ℃ to 80 ℃.
  8. 8. A supported Taniaphos catalyst characterized in that it is prepared by the process of any one of claims 1-7.
  9. 9. A supported Taniaphos catalyst is characterized in that, the supported Taniaphos catalyst has the following general formula: ; Wherein a is 1 and b is 1-75; R is selected from methyl, phenyl, benzyl, benzhydryl, 3, 5-diphenyl, X is selected from methylene, ethyl, chloromethyl, bromomethyl, dichloromethyl and dibromomethyl.
  10. 10. Use of a supported Taniaphos catalyst according to any of claims 8-9 in a non-para-allylic alkylation reaction.

Description

Preparation method of Taniaphos-supported catalyst by solvent weaving method Technical Field The invention belongs to the technical field of organic chemistry, and particularly relates to a preparation method of a solvent braiding method supported Taniaphos catalyst. Background The Taniaphos ligand is a classical chiral micromolecular ferrocene ligand, can coordinate with various metals such as ruthenium, rhodium, iridium, copper and the like to form a chiral metal complex catalyst with high catalytic activity, and is widely applied to various asymmetric reactions. So far, taniaphos-metal complex catalysts have been successfully used for the construction of chiral carbon-nitrogen, carbon-oxygen, carbon-hydrogen, carbon-boron, carbon-sulfur, carbon-phosphorus, carbon-selenium bonds and exhibit excellent catalytic activity and higher stability. However, the preparation of Taniaphos ligands is relatively complex and generally requires multiple steps to obtain the final product. In the synthesis process, high-risk chemical reagents such as tertiary butyl lithium and the like are needed, and strict requirements are also provided for harsh conditions such as anhydrous and anaerobic conditions, so that the Taniaphos ligand has high use cost and is severely limited in application in industrial scale. In addition, the taniahos ligand and the metal complex thereof have better solubility in organic solvents, so that the taniahos ligand and the metal complex thereof are difficult to effectively separate after homogeneous catalysis reaction, residual metal/ligand complex not only can cause poisoning of subsequent reaction, but also has serious metal residual problem, and after the reaction is finished, the catalyst and the product are usually separated through complicated purification steps such as column chromatography and the like, so that the purification difficulty of the product is greatly increased. In order to solve the problems, the loading of the catalyst is one of the important directions of higher use cost of chiral micromolecular catalysts at present, and by loading the catalyst, the simple separation of products and the repeated recycling of the catalyst can be realized theoretically. However, most of the currently reported Taniaphos catalyst loading schemes have significant limitations. Traditional loading strategies rely primarily on multi-step chemical modification of taniahos ligands, typically requiring the introduction of specific functional groups (e.g., hydroxyl, amino or thiol groups) onto the catalyst, which are then used to react or polymerize with the support to effect loading of the catalyst, and the additional reaction steps in the multi-step modification scheme not only result in a decrease in the overall yield of the product, but also result in a more complex synthetic route, further increasing the cost of use of the catalyst, contrary to the initial objective of reducing catalyst cost by loading. More importantly, chemical modifications may alter the electronic properties and spatial structure of the ligand, thereby affecting its chiral inducibility, resulting in reduced catalytic activity and enantioselectivity. Alternatively, there are reports of a one-step grafting method of silica without modification to support the chiral catalyst. This process typically involves pretreatment of commercial silica supports, introduction of specific anionic functionalities, and subsequent incorporation of cationic metal centers in the catalyst by ion pair interactions. However, commercial silica supports are relatively single in type, including common silica gel powders, MCM-41 and SBA-15 mesoporous silica. The catalyst structure is unstable due to weak interaction of the ion pairs, and obvious deactivation is accompanied in the reaction process. In addition, the distribution of active sites is difficult to control due to the non-uniformity of the surface of the carrier, so that the activity of the supported catalyst is also reduced to a certain extent compared with that of a homogeneous phase. Therefore, the development of the preparation method of the Taniaphos supported catalyst with various structures and simple methods has important research value. The solvent weaving method is a preparation method of the super-crosslinked polymer based on the Friedel-crafts alkylation reaction, the method has simple reaction conditions and wide sources of polymerized monomers, and the obtained super-crosslinked polymer has various structures and larger academic and application research values. However, the Lwis acid catalyst used in the method and the high temperature condition lead to high reactivity, which may damage the structure of the chiral small molecule catalyst. Second, the reaction sites of the friedel-crafts alkylation reaction are not single, and a series of polysubstituted products are usually generated, which may cause chiral centers of the catalyst to change during the loading process, and finally th