Method for preparing aryl boronate at room temperature

An aryl borate, room temperature technology, applied in the field of preparing aryl borate at room temperature, can solve the problems of unsuitable large-scale preparation, harsh reaction conditions, large catalyst dosage, etc., and achieves a wide range of applications, mild reaction conditions, and compatibility. good effect

Active Publication Date: 2019-04-30
GUANGZHOU MEDICAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the palladium-catalyzed method has been well applied in the synthesis of arylboronic esters using aryl halides (mainly bromides and iodides) or aryl triflates, the reactions all need to be carried out in anhydrous anhydrous It is carried out under oxygen, high temperature, and sealed tube conditions, and has disadvantages such as harsh reaction conditions, large amount of catalyst, and unsuitable for mass production.

Method used

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  • Method for preparing aryl boronate at room temperature
  • Method for preparing aryl boronate at room temperature
  • Method for preparing aryl boronate at room temperature

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Embodiment 1: the synthesis of 4-tert-butylphenylboronic acid pinacol ester

[0021]

[0022] Method (1): take 4-tert-butylchlorobenzene as raw material synthesis: add K in the reaction flask successively 3 PO 4 ·7H 2 O (3.0g, 8.85mmol), bis-pinacol borate (749mg, 2.95mmol), catalyst chlorine (2-dicyclohexylphosphino-2',4',6'-tri-isopropyl- 1,1'-biphenyl)(2'-amino-1,1'-biphenyl-2-yl)palladium(II) (12mg, 0.015mmol) and the ligand 2-dicyclohexylphosphine-2', 4′,6′-Triisopropylbiphenyl (4mg, 0.008mmol), then add EtOH (6mL) and stir well, add p-tert-butylchlorobenzene (0.5mL, 2.95mmol), react at room temperature for 0.5h, wait After the reaction, the reaction solution was diluted with ethyl acetate (2 mL), filtered through diatomaceous earth to remove insoluble matter, ethyl acetate (6 mL) was washed three times, the filtrate was combined, concentrated under reduced pressure to remove the solvent, and filtered with silica gel (200 ~ 300 mesh) was separated by column ...

Embodiment 2

[0024] Embodiment 2: the synthesis of 3-methoxyphenylboronic acid pinacol ester

[0025]

[0026] Method (1): Taking 3-methoxychlorobenzene as raw material synthesis: the method (1) of reference example 1, the difference is that the p-tert-butylchlorobenzene used uses equimolar 3-methoxychlorobenzene Benzene was replaced, other steps were the same as the method (1) of Example 1, and the obtained white solid was identified as 3-methoxyphenylboronic acid pinacol ester by NMR spectrum, and the yield was 92%. 1 H NMR (300MHz, CDCl 3 )δ (ppm): 7.41 (m, 1H), 7.33 (d, J = 3.5Hz, 1H), 7.29 (s, 1H), 7.01 (ddd, J 1 =8.2Hz,J 2 =2.8Hz,J 3 =1.2Hz,1H),3.84(s,3H),1.35(s,12H); 13 C NMR (75MHz, CDCl 3 )δ (ppm): 159.2, 129.1, 127.4, 118.9, 118.1, 84.2, 55.4, 25.1.

[0027] Method (2): taking 3-methoxy bromobenzene as raw material synthesis: with reference to the method (1) of this embodiment, the difference is that the 3-methoxy chlorobenzene used uses equimolar 3-methoxy bromide Benz...

Embodiment 3

[0028] Embodiment 3: the synthesis of 4-hydroxymethylphenylboronic acid pinacol ester

[0029]

[0030] Method (1): taking 4-chlorobenzyl alcohol as raw material synthesis: the method (1) of reference example 1, the difference is that used p-tert-butylchlorobenzene is replaced with equimolar 4-chlorobenzyl alcohol, and the reaction The time was 2 hours, and other steps were the same as the method (1) of Example 1, and the obtained white solid was identified as 4-hydroxymethylphenylboronic acid pinacol ester by NMR spectrum, and the yield was 96%. 1 H NMR (300MHz, CDCl 3)δ (ppm): 7.78 (dd, J 1 =12.8Hz,J 2 =8.1Hz,2H),7.38(dd,J 1 =12.8Hz,J 2 =8.1Hz, 2H), 4.70(s, 2H), 1.35(s, 12H); 13 C NMR (75MHz, CD 3 OD) 146.2, 136.0, 127.2, 85.2, 65.2, 25.3.

[0031] Method (2): taking 4-iodobenzyl alcohol as raw material synthesis: with reference to the method (1) of this embodiment, the difference is that the 4-chlorobenzyl alcohol used is replaced with equimolar 4-iodobenzyl alcoh...

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Abstract

The invention discloses a method for preparing aryl boronate represented by a formula I at a room temperature. The method comprises: carrying out a reaction on a diboron compound represented by a formula II and an aryl halide in an organic solvent for 0.5-8 h at a room temperature under the actions of an alkali, a chloro(2-dicyclohexylphosphino-2',4',6'-tri-isopropyl-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-2-yl)palladium (II) catalyst and a 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl ligand, and carrying out post-treatment to obtain the corresponding aryl boronate. According to the present invention, the method has characteristics of mild reaction conditions, simple operation, wide application range, good compatibility with various functional groups on aryl, high efficiency and economy, can achieve high yield of aryl borate under normal pressure and normal pressure conditions, and is suitable for large-scale preparation of aryl borate. The formulas I and II are defined in the specification, wherein R' represents any one selected from phenyl with substituent, pyridyl, thienyl, indyl, pyrazolyl and naphthyl.

Description

Technical field: [0001] The invention relates to the field of organic chemical synthesis, in particular to a method for preparing aryl borate at room temperature. Background technique: [0002] Arylboronate compounds are a class of stable, low-toxic and important intermediates in organic synthesis, which are widely used in transition metal-catalyzed carbon-carbon bond coupling and carbon-heteroatom coupling reactions. Such compounds are not only used as coupling agents for the synthesis of fine chemicals, drugs, and pesticides, but also as welding agents, multifunctional lubricants, and flame retardants, etc., and have great demand in the fields of organic synthesis, medicine, and materials. The traditional method of synthesizing aryl boronic acid or borate is Grignard reagent and lithium reagent method, that is, using aryl bromide or iodide for metallization, preparing the corresponding Grignard reagent or organolithium reagent and then using boron reagent. boronation reac...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 季红易涛张超张建业吴丽阳蔡江红
Owner GUANGZHOU MEDICAL UNIV
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