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Method for synthesizing alkenyl borate compound through transfer boronation

A technology of alkenyl boronic acid esters and compounds, applied in the fields of organic synthesis and metal catalysis, can solve the problems of borane sensitivity to water and oxygen, difficulty in obtaining substrates, poor compatibility of chemoselective functional groups, etc., and achieve high reaction efficiency and easy operation , the effect of good functional group compatibility

Active Publication Date: 2019-11-05
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the reported synthetic methods have disadvantages such as poor chemoselectivity and functional group compatibility; difficult to obtain substrates; borane is sensitive to water and oxygen.

Method used

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  • Method for synthesizing alkenyl borate compound through transfer boronation
  • Method for synthesizing alkenyl borate compound through transfer boronation
  • Method for synthesizing alkenyl borate compound through transfer boronation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1 A method for synthesizing alkenyl boronate compounds by transfer borylation reaction:

[0024]

[0025] Add p-methylstyrene 1a (0.2 mmol, 25 μL), styrene borate pinacol ester 2a (0.4 mmol, 92 mg), toluene (1 mL), Cp 2 ZrH 2 (0.01 mmol, 2.3 mg), stirred reaction at 130 ℃ under nitrogen (1 atm) atmosphere. GC detection until the completion of the reaction 18h. Diatomaceous earth filtration, the solvent was spin-dried under reduced pressure, and the residue was purified by silica gel column chromatography, using petroleum ether: ethyl acetate (100 mL: 1 mL) as the eluent to obtain p-methylstyrene as a colorless oil Pinacol borate 3a (39 mg, 80%).

[0026] The characterization data of this compound are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.40 – 7.36(m, 3H), 7.15 – 7.14 (m, 2H), 6.12 (d, J = 18.4 Hz, 1H), 2.35 (s, 3H), 1.32(s, 12H). 13 C NMR (101 MHz, Chloroform- d ) δ 149.5, 138.9, 134.8, 129.3, 127.0, 83.2, 24.8, 21.3. 11 B NMR (128 MHz, ...

Embodiment 2

[0027] Example 2 A method for synthesizing alkenyl boronate compounds by transfer borylation reaction:

[0028]

[0029] Add p-methylstyrene 1a (0.2 mmol, 25 μL), styrene borate pinacol ester 2a (0.4 mmol, 92 mg), toluene (1 mL), Cp 2 ZrH 2 (0.01 mmol, 2.3 mg), stirred reaction at 130 ℃ under argon (1 atm) atmosphere. GC detection until the completion of the reaction 18h. Diatomaceous earth filtration, the solvent was spin-dried under reduced pressure, and the residue was purified by silica gel column chromatography, using petroleum ether: ethyl acetate (100 mL: 1 mL) as the eluent to obtain p-methylstyrene as a colorless oil Pinacol borate 3a (40 mg, 82%).

[0030] The characterization data of this compound are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.40 – 7.36(m, 3H), 7.15 – 7.14 (m, 2H), 6.12 (d, J = 18.4 Hz, 1H), 2.35 (s, 3H), 1.32(s, 12H). 13 C NMR (101 MHz, Chloroform- d ) δ 149.5, 138.9, 134.8, 129.3, 127.0, 83.2, 24.8, 21.3. 11 B NMR (128 MHz, Chl...

Embodiment 3

[0031] Example 3 A method for synthesizing alkenyl boronate compounds by transfer borylation reaction:

[0032]

[0033] Add p-methylstyrene 1a (0.2 mmol, 25 μL), styrene borate pinacol ester 2a (0.4 mmol, 92 mg), toluene (1 mL), Cp 2 ZrH 2 (0.01 mmol, 2.3 mg), stirred reaction at 60 ℃ under nitrogen (1 atm) atmosphere. GC detection until the completion of the reaction 36h. Diatomaceous earth filtration, the solvent was spin-dried under reduced pressure, and the residue was purified by silica gel column chromatography, using petroleum ether: ethyl acetate (100 mL: 1 mL) as the eluent to obtain p-methylstyrene as a colorless oil Pinacol borate 3a (15 mg, 30%).

[0034] The characterization data of this compound are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.40 – 7.36(m, 3H), 7.15 – 7.14 (m, 2H), 6.12 (d, J = 18.4 Hz, 1H), 2.35 (s, 3H), 1.32(s, 12H). 13 C NMR (101 MHz, Chloroform- d ) δ 149.5, 138.9, 134.8, 129.3, 127.0, 83.2, 24.8, 21.3. 11 B NMR (128 MHz, C...

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Abstract

The invention relates to a method for synthesizing an alkenyl borate compound by a transfer boronation. The method comprises the steps that substituted olefin and styrene boronic acid pinacol ester are dissolved into a solvent, then a zirconium catalyst is added, in a protective atmosphere, reacting is carried out at 60-150 DEG C for 8-36 hours, and then separating is conducted to obtain the styrene boronic acid pinacol ester compound. The method is easy to operate and low in cost, use of diborane and excessive olefin is avoided, and the obtained alkenyl borate compound can be applied to medical synthetic intermediates and organic photoelectric material science.

Description

technical field [0001] The invention relates to the technical field of organic synthesis and metal catalysis, in particular to a method for synthesizing alkenyl boronate compounds through transfer borylation reaction. Background technique [0002] Alkenyl boronic acid ester compounds are an important class of organic synthesis intermediates, which can be used to construct C-C and C-X (X= F, Cl, Br, I, O, N, etc.), and widely exist in biological and potential pharmaceuticals. Among the active compounds, it has important research significance and application value in the fields of organic chemistry and drug development. Recent findings have also revealed potential medicinal properties of alkenyl borates. [0003] Given their importance, new methods for the synthesis of this class of compounds have now been developed. Generally, alkenyl borates are synthesized by transition metal-catalyzed hydroboration of alkynes or by transmetallation of alkenyl lithium / magnesium reagents w...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 吴立朋师晓楠
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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