Search

CN-121990867-A - Method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne under catalysis of palladium

CN121990867ACN 121990867 ACN121990867 ACN 121990867ACN-121990867-A

Abstract

The invention discloses a method for catalyzing cyclization reaction of 2-biphenyl fluorosulfonate compounds and alkyne by palladium, which comprises the steps of taking 2-biphenyl fluorosulfonate with a structure shown in (I) as a raw material, adding alkyne, palladium catalyst, ligand, alkali and solvent in a formula (II) into a reactor to prepare phenanthrene compounds shown in (III): substituent R 1 、R 2 is independently selected from hydrogen, chloro, fluoro, methyl, methoxy, trifluoromethyl, isopropyl, phenyl, cyano, tert-butyl or naphthyl, and substituent R 3 、R 4 is independently selected from methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-ketophenyl. The invention uses the simple and easily obtained 2-biphenyl fluoro sulfonate compounds as raw materials, and can obtain the corresponding phenanthrene compounds with better yield.

Inventors

  • DING CHENGRONG
  • ZHANG SHUAI
  • Guan Chenfei
  • ZHANG GUOFU
  • Mou xuan

Assignees

  • 浙江工业大学

Dates

Publication Date
20260508
Application Date
20260119

Claims (10)

  1. 1. A method for carrying out cyclization reaction on a palladium-catalyzed 2-biphenyl fluorosulfonate compound and alkyne, which is characterized by comprising the following steps: 2-biphenyl fluorosulfonate compounds shown in formula (I) are used as raw materials, alkyne shown in formula (II), palladium catalyst, ligand, alkali and solvent are added into a reactor to prepare phenanthrene compounds shown in formula (III), and the reaction formula is as follows: , The substituents R 1 、R 2 in formula (I) and formula (III) are each independently selected from hydrogen, chloro, fluoro, methyl, methoxy, trifluoromethyl, isopropyl, phenyl, tert-butyl, cyano or naphthyl, and the substituents R 3 、R 4 in formula (II) and formula (III) are each independently selected from methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-ketophenyl.
  2. 2. The method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne through palladium catalysis according to claim 1, wherein the molar ratio of the 2-biphenyl fluorosulfonate compounds shown in formula (I) to alkyne shown in formula (II) is 1:1-20.
  3. 3. The method for carrying out cyclization reaction on 2-diphenyl fluorosulfonate compounds and alkyne by using palladium as catalyst in claim 1, wherein the molar ratio of the 2-diphenyl fluorosulfonate compounds shown in formula (I) to palladium catalyst is 1:0.05-0.2.
  4. 4. The method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne by using palladium as catalyst in claim 1, wherein the molar ratio of the 2-biphenyl fluorosulfonate compounds shown in formula (I) to ligand is 1:0.05-0.2.
  5. 5. The method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne by using palladium as catalyst in claim 1, wherein the molar ratio of the 2-biphenyl fluorosulfonate compounds shown in formula (I) to alkali is 1:1-5.
  6. 6. The method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne by using palladium as catalyst in claim 1, wherein the molar ratio of the 2-biphenyl fluorosulfonate compounds shown in formula (I) to the solvent is 1:1-30.
  7. 7. The method for carrying out cyclization reaction on 2-diphenyl fluorosulfonate compounds and alkyne by using palladium as claimed in claim 1, wherein the reaction temperature is 70-150 ℃ and the reaction time is 8-22 h.
  8. 8. The method for carrying out cyclization reaction on 2-diphenyl fluorosulfonate compound and alkyne according to claim 1, wherein the palladium catalyst is Pd (OAc) 2 、Pd(dba) 2 、PdCl 2 or Pd (PPh 3 ) 2 Cl 2 ), and the ligand is triphenylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1 '-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2', 6 '-dimethoxybiphenyl or 2,2' -bipyridine.
  9. 9. The method for carrying out cyclization reaction on 2-diphenyl fluorosulfonate compound and alkyne by palladium catalysis according to claim 1, wherein the base is CsF, DBU, n-Pr 2 NH、n-Et 2 NH or n-Me 2 NH in THF.
  10. 10. The method for carrying out cyclization reaction on 2-diphenyl fluorosulfonate compound and alkyne by palladium catalysis according to claim 1, wherein the solvent is 1,4-Dioxane, DCE, DMF or DMSO.

Description

Method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne under catalysis of palladium Technical Field The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for carrying out cyclization reaction on a palladium-catalyzed 2-biphenyl fluorosulfonate compound and alkyne. Background The phenanthrene compound is polycyclic aromatic hydrocarbon containing three benzene rings, and can be used for aspects of synthetic resin, plant growth hormone, vat dye, tanning material and the like. To date, nearly hundred natural phenanthrenes have been isolated, but only from eight species, including Shan Fei, biphenanthrene and phenanthridine. Many of the isolated compounds are vinyl substituted. Therefore, it is particularly important to develop a new synthesis method of phenanthrene compounds. The synthesis method of the aryl ether compound reported in the literature mainly comprises (1) converting aromatic hydrocarbon into triphenyl through effective palladium (0) catalyzed cyclotrimerization reaction, thereby proving the possibility. The preparation of phenanthrene compounds by co-cyclizing alkynes and alkynes is realized, the tolerance of functional groups is poor, and the substitution of groups is limited. (2) Coupling various alkynes with diaryl related grignard reagent oxidative coupling conditions allow the reaction to proceed with significant chemoselectivity, but the potential problems of the grignard reagents limit its use. (3) Phenanthrene can be synthesized by radical initiator, photocatalyst and electrocatalysis, but there are problems of severe conditions and poor functional group tolerance. The fluorosulfonate group (-OSO 2 F) possesses reactivity similar to-OTf, bromide or chloride, and is an easy leaving group. At present, -OSO 2 F has been widely used for various types of chemical transformations including reduction, metal-catalyzed cross-coupling, deoxofluorination, amination, methoxycarbonylation, and the like. Disclosure of Invention The invention provides a method for carrying out cyclization reaction on 2-biphenyl fluorosulfonate compounds and alkyne by palladium catalysis aiming at the defects in the prior art, in order to achieve the purpose, the invention selects the method for preparing the phenanthrene compound by efficiently promoting the cyclization reaction of the 2-biphenyl fluorosulfonate compound and alkyne by using the palladium catalyst. The invention relates to a method for preparing phenanthrene compounds by palladium catalysis by using cheap and easily available fluorosulfonate with high stability as a raw material. The technical scheme adopted by the invention is as follows: A method for carrying out cyclization reaction on a palladium-catalyzed 2-biphenyl fluorosulfonate compound and alkyne, which comprises the following steps: 2-biphenyl fluorosulfonate compounds shown in formula (I) are used as raw materials, alkyne shown in formula (II), palladium catalyst, ligand, alkali and solvent are added into a reactor to prepare phenanthrene compounds shown in formula (III), and the reaction formula is as follows: , The substituents R 1、R2 in formula (I) and formula (III) are each independently selected from hydrogen, chloro, fluoro, methyl, methoxy, trifluoromethyl, isopropyl, phenyl, tert-butyl, cyano or naphthyl, and the substituents R 3、R4 in formula (II) and formula (III) are each independently selected from methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-ketophenyl. Further, the molar ratio of the 2-biphenyl fluorosulfonate compound shown in the formula (I) to alkyne shown in the formula (II) is 1:1-20. Further, the molar ratio of the 2-biphenyl fluorosulfonate compound shown in the formula (I) to the palladium catalyst is 1:0.05-0.2. Further, the molar ratio of the 2-biphenyl fluorosulfonate compound shown in the formula (I) to the ligand is 1:0.05-0.2. Further, the molar ratio of the 2-biphenyl fluorosulfonate compounds shown in the formula (I) to the alkali is 1:1-5. Further, the molar ratio of the 2-biphenyl fluorosulfonate compound shown in the formula (I) to the solvent is 1:1-30. Further, the reaction temperature is 70 oC~150o ℃ and the reaction time is 8-22 h. Further, the palladium catalyst is Pd (OAc) 2、Pd(dba)2、PdCl2 or Pd (PPh 3)2Cl2, the ligand is triphenylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1 '-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2', 6 '-dimethoxybiphenyl or 2,2' -bipyridine. Further, the base is CsF, DBU, n-Pr 2NH、n-Et2 NH or n-Me 2 NH in THF. Further, the solvent is 1,4-Dioxane, DCE, DMF or DMSO. The beneficial effects of the invention are mainly as follows: 1) The invention has the advantages of easily obtained raw materials and high selectivity under the synergistic effect of the palladium catalyst and the ligand. 2) The method has wide tolerance of functional grou