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Application of o-methyl-anilino lithium in catalysis of aldehyde and borane hydroboration

A technology of o-methylanilino and methylanilino, which is applied in the application field of o-toluidine lithium in catalyzing the hydroboration reaction of aldehydes and boranes, can solve the problems of harsh reaction conditions and expensive catalysts, and achieve the goal of reaction Short time, good universality, simple and controllable effect

Inactive Publication Date: 2018-10-16
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the catalytic systems reported so far, the catalysts are relatively expensive, or the reaction conditions are relatively harsh. Therefore, it is particularly urgent to develop a new catalytic system that can efficiently catalyze the hydroboration reaction of aldehydes under mild conditions.

Method used

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  • Application of o-methyl-anilino lithium in catalysis of aldehyde and borane hydroboration
  • Application of o-methyl-anilino lithium in catalysis of aldehyde and borane hydroboration
  • Application of o-methyl-anilino lithium in catalysis of aldehyde and borane hydroboration

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Example 1: Lithium o-methylanilide catalyzes the hydroboration reaction of benzaldehyde and pinacol borane

[0029] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) of lithium o-toluidine under the protection of argon (0.1 mol% dosage, the same below), then add 0.1596 mL of borane with a syringe, and mix well , then add 0.1016 mL of benzaldehyde with a syringe, and the mixture is stirred at room temperature. After reacting for 10 min, the NMR yield is 99%. After that, a small amount of tetrahydrofuran and excess borane are removed under reduced pressure to obtain the corresponding pinacol boronic acid Ester C 6 h 5 CH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.36-7.23 (m, 5H, Ar-H), 4.92 (s, 2H, OCH 2 ), 1.26 (s, 12H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 138.76 (Ar-C), 127.81 (Ar-C), 126.89 (Ar-C), 126.24 (Ar-C), 82.48 (OC), 66.20 (OCH 2 ), 24.15 (CH 3 ).

[0030] Substituti...

Embodiment 2

[0032] Example 2: Hydroboration reaction of p-fluorobenzaldehyde and pinacol borane catalyzed by lithium o-toluide

[0033] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) (0.1 mol% dosage) of o-toluidine lithium under the protection of argon, then add 0.1596 mL of borane with a syringe, mix well, and then use 0.1072 mL of p-fluorobenzaldehyde was added into the syringe, and the mixture was stirred at room temperature. After 10 minutes of reaction, the NMR yield was 99%. After that, a small amount of tetrahydrofuran and excess borane were removed under reduced pressure to obtain the corresponding pinacol borate p -F-C 6 h 4 CH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.34-7.29 (m, 2H, Ar-H), 7.04-6.98 (m, 2H, Ar-H), 4.87 (s, 2H, OCH2), 1.26 (s, 12H, CH3). 13 C NMR (101 MHz, CDCl 3 ) δ161.71 (ds, Ar-C), 134.50 (d, J = 3.2 Hz, Ar-C), 128.14 (d, J = 8.1 Hz, Ar-C), 114.60 (ds, Ar-C), 82...

Embodiment 3

[0034] Example 3: Lithium o-methylanilide catalyzes the hydroboration reaction of m-chlorobenzaldehyde and pinacol borane

[0035] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) (0.1 mol% dosage) of o-toluidine lithium under the protection of argon, then add 0.1596 mL of borane with a syringe, mix well, and then use Add 0.0899 mL of m-chlorobenzaldehyde into the syringe, and stir the mixture at room temperature. After 10 minutes of reaction, the NMR yield is 99%. After that, a small amount of tetrahydrofuran and excess borane are removed under reduced pressure to obtain the corresponding pinacol borate m -Cl-C 6 h 4 CH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.36 (s, 1H, Ar-H), 7.28-7.19 (m, 3H, Ar-H), 4.89 (s, 2H, OCH 2 ), 1.27 (s, 12H,CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 140.75(Ar-C), 133.75 (Ar-C), 129.08 (Ar-C), 126.99 (Ar-C), 126.30 (Ar-C), 124.17(Ar-C), 82.61 (OC), 65.41 (OC...

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Abstract

The invention discloses application of o-methyl-anilino lithium in the catalysis of aldehyde and borane hydroboration. Borane is added into a reaction bottle that is dewatered and deoxidized in an inert gas atmosphere in an anhydrous oxygen-free environment; the catalyst, o-methyl-anilino lithium, is added; mixing is performed well before an aldehyde is added; hydroboration is carried out; the reaction is ended after exposure to air so as to obtain borates; the aldehyde is selected from aromatic aldehydes and heterocyclic aldehydes. The catalyst disclosed herein is well applicable to aromaticaldehydes and heterocyclic aldehydes having different substitution positions and electronic effects; more choices are provided to attain borates with different substituent structures.

Description

technical field [0001] The application of the o-toluide lithium involved in the present invention specifically relates to the application of the o-toluide lithium in catalyzing the hydroboration reaction of aldehyde and borane. technical background [0002] Since Brown et al. discovered in 1956 that borohydride catalyzed the hydroboration reaction of olefins, the hydroboration reaction of unsaturated bonds has become a very effective means for the preparation of various organic synthesis intermediates. The research on hydrogenation reaction is of great significance to both modern industry and organic synthetic chemistry, which has attracted extensive attention of scientific researchers. [0003] A variety of catalysts have been used for the hydroboration of aldehydes, and especially in recent years, there have been numerous reports of such reactions. Due to the absence of catalysts, the hydroboration reaction of carbonyl compounds is difficult to occur. Therefore, the focu...

Claims

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Application Information

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IPC IPC(8): C07F5/04B01J31/02
CPCC07F5/04B01J31/0252B01J2231/344
Inventor 薛明强朱章野武振杰洪玉标蔡玲霞沈琪
Owner SUZHOU UNIV
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