Application of n-butyllithium in catalyzing hydroboration of aldehyde and borane

A technology of n-butyl lithium and hydroboration, which is applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of expensive catalysts and harsh reaction conditions, etc. Achieve good universality, short reaction time and mild reaction conditions

Inactive Publication Date: 2018-08-17
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, the focus of research on this type of reaction is to develop an efficient catalytic system; however, the catalysts of the reported catalytic systems are relatively expensive, or the reaction conditions are relatively harsh. Catalytic systems for hydrogenation reactions are particularly urgent

Method used

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  • Application of n-butyllithium in catalyzing hydroboration of aldehyde and borane
  • Application of n-butyllithium in catalyzing hydroboration of aldehyde and borane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Example 1: Hydroboration of benzaldehyde and pinacol borane catalyzed by n-butyllithium

[0028] In the dehydration and deoxygenation reaction flask, under the protection of argon, add 20 ul n-butyllithium tetrahydrofuran solution (0.05M) (0.1 mol% dosage, the same below), then add 0.1596 mL borane with a syringe, mix well, Add 0.1016 mL of benzaldehyde with a syringe, and stir the mixture at room temperature. After 10 minutes of reaction, the NMR yield is 99%. Afterwards, it is treated under reduced pressure to remove a small amount of tetrahydrofuran and excess borane to obtain the corresponding pinacol boron 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 ).

[0029] Replacing n-butyllithium with the amide lithium compound of f...

Embodiment 2

[0031] Example 2: Hydroboration of p-fluorobenzaldehyde and pinacol borane catalyzed by n-butyllithium

[0032] In the reaction flask that has been dehydrated and deoxygenated, add 20 ul of n-butyllithium tetrahydrofuran solution (0.05M) (0.1 mol% dosage, the same below) under the protection of argon, then add 0.1596 mL of borane with a syringe, mix well, Add 0.1072 mL of p-fluorobenzaldehyde with a syringe, and stir the mixture at room temperature. After 10 minutes of reaction, the NMR yield is 99%. Afterwards, treat under reduced pressure to remove a small amount of tetrahydrofuran and excess borane to obtain the corresponding pina alcohol 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 )δ 161.71 (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), 82.54 (OC), 65.56 (OCH 2 ...

Embodiment 3

[0033] Example Three: n-Butyl Lithium Catalyzed Hydroboration Reaction of m-Chlorobenzaldehyde and Pinacol Borane

[0034] In the reaction flask that has been dehydrated and deoxygenated, add 20 ul of n-butyllithium tetrahydrofuran solution (0.05M) (0.1 mol% dosage, the same below) under the protection of argon, then add 0.1596 mL of borane with a syringe, mix well, Add 0.0899 mL of m-chlorobenzaldehyde with a syringe, and stir the mixture at room temperature. After 10 minutes of reaction, the NMR yield is 99%. Afterwards, it is treated under reduced pressure to remove a small amount of tetrahydrofuran and excess borane to obtain the corresponding pina alcohol 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 ) δ140.75 (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...

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Abstract

The invention discloses application of n-butyllithium in catalyzing hydroboration of aldehyde and borane, a method of hydroboration comprises the following steps of in a water-free and oxygen-free environment, under the inert gas atmosphere, adding borane into a reaction bulb subjected to dehydration and deoxidization treatment, then adding a catalyst n-butyllithium, uniformly mixing, then addingaldehyde to perform hydroboration. Exposing to the air to stop the reaction after the reaction is finished, so as to obtain a product. The catalyst disclosed by the invention has better universality to aromatic aldehyde with different replace positions and different electronic effects as well as to heterocyclic aldehydes and fatty aldehyde, and more choice can be provided for obtaining boric acidester compounds with different substituent group structures.

Description

technical field [0001] The invention relates to the application of commercial reagent n-butyl lithium, in particular to the efficient application of n-butyl lithium in catalyzing the hydroboration reaction of aldehyde and borane. technical background [0002] Since Brown et al. discovered in 1956 that borohydrides catalyzed the hydroboration of alkenes, the hydroboration of unsaturated bonds has become a very effective means for the preparation of various organic synthesis intermediates. As for the borate compound itself, the product of hydroboration reaction, it can not only be used as polymer additives, gasoline additives, flame retardants, and sterilizers, but also as special surfactants, lubricating oil additives, and automobile brake fluids. , a wide range of applications. For the hydroboration reaction of equivalent catalyzed carbonyl compounds, the hydrolysis of the obtained boric acid ester products is also a very effective method for synthesizing alcohols in contem...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/12C07F5/04
CPCB01J31/122C07F5/04
Inventor 薛明强朱章野徐晓娟武振杰洪玉标沈琪
Owner SUZHOU UNIV
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