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Application of n-butyllithium in catalytic hydroboration of ketone and borane

A technology of n-butyllithium and hydroboration, which is applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problems of expensive catalysts and harsh reaction conditions, etc. Achieve good universality, short reaction time and high reaction yield

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 currently reported, the catalysts are relatively expensive, or the reaction conditions are relatively harsh. In addition, although they belong to carbonyl compounds, ketones and aldehydes have different reaction properties. However, only one raw material reaction occurs; therefore, it is particularly urgent to develop a new catalytic system that efficiently catalyzes the hydroboration reaction of ketones under mild conditions.

Method used

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  • Application of n-butyllithium in catalytic hydroboration of ketone and borane
  • Application of n-butyllithium in catalytic hydroboration of ketone and borane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1: Hydroboration of acetophenone and pinacol borane catalyzed by n-butyllithium

[0027] 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), then add 0.1596 mL borane with a syringe, mix well, and then use a syringe Add 0.1167 mL of acetophenone, and stir the mixture at room temperature. After 20 min 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 borate . C 6 h 5 CH(CH 3 )OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.38-7.21 (m, 5H, Ar-H), 5.24 (q, J = 6.5Hz, 1H, OCH), 1.49 (d, J = 6.5 Hz, 3H, CH 3 ), 1.22 (d, J = 11.9 Hz, 12H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 144.09 (Ar-C), 127.71 (Ar-C), 126.62 (Ar-C), 124.86(Ar-C), 82.26 (OC), 72.10 (OCH), 24.98 (CH 3 ), 24.07 (d, J = 4.5 Hz, CH...

Embodiment 2

[0030] Example 2: Hydroboration of p-fluoroacetophenone and pinacol borane catalyzed by n-butyllithium

[0031] 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), then add 0.1596 mL borane with a syringe, mix well, and then use a syringe 0.1208 mL of p-fluoroacetophenone was added, and the mixture was stirred at room temperature. After 20 min of reaction, the NMR yield was 99%, and then treated under reduced pressure to remove a small amount of tetrahydrofuran and excess borane to obtain the corresponding pinacol boron esters. 1 H NMR (400 MHz, CDCl 3 ) δ 7.35-7.30 (m, 2H, Ar-H), 7.02-6.96 (m, 2H, Ar-H), 5.22 (q, J = 6.4Hz, 1H, OCH), 1.47 (d, J = 6.5 Hz, 3H, CH 3 ), 1.22 (d, J = 11.6 Hz, 12H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 161.94 (ds, Ar-C), 140.34 (d, J = 3.1 Hz, Ar-C),127.02 (d, J = 8.0 Hz, Ar-C), 114.93 (ds, Ar-C), 82.80 (OC), 72.00 (OCH), 25.4...

Embodiment 3

[0032] Example 3: Hydroboration reaction of m-fluoroacetophenone and pinacol borane catalyzed by n-butyllithium

[0033] 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), then add 0.1596 mL borane with a syringe, mix well, and then use a syringe Add 0.1226 mL of m-fluoroacetophenone, and stir the mixture at room temperature. After 20 min 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 esters. 1 H NMR (400 MHz, CDCl 3 ) δ 7.29-7.24 (m, 1H, Ar-H), 7.12-7.08 (m, 2H, Ar-H), 6.94-6.89 (m, 1H,Ar-H), 5.23 (q, J = 6.4 Hz, 1H, OCH), 1.48 (d, J = 6.5 Hz, 3H, CH 3 ), 1.23 (d, J = 11.4 Hz, 12H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 162.85 (ds, Ar-C), 147.26(d,J = 6.9 Hz, Ar-C), 129.67 (d, J = 8.2 Hz, Ar-C), 120.88 (d, J = 2.8 ...

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Abstract

The invention discloses an application of n-butylllithium in catalytic hydroboration of ketone and borane. The n-butyllithium is a commercial n-butyl lithium reagent, and the method includes: adding borane to a reaction flask subjected to dehydration and deoxygenation treatment without oxygen and water at inert gas atmosphere; adding a catalyst n-butyllithium with even mixing prior to adding ketone for hydroboration. The catalyst has good universality to aromatic ketones with different substitution positions and different electron effects as well as heterocyclic ketone and aliphatic ketone, and more choices for borate compounds with different substituent structures are provided.

Description

technical field [0001] The application of n-butyllithium involved in the present invention specifically relates to the efficient application of n-butyllithium in catalyzing the hydroboration reaction of ketone 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 contemporary o...

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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