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Application of deprotonated phenyl bridged beta-ketimine lithium complex in cyanosilylation reaction

A technology of lithium ketimide and phenyl bridge, applied in lithium complexes and in the field of organic synthesis, can solve the problems such as no reports, and achieve the effects of easy synthesis, mild temperature and simple structure

Pending Publication Date: 2020-11-27
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There is no report about the complexes of dianionic β-ketoimine ligands so far

Method used

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  • Application of deprotonated phenyl bridged beta-ketimine lithium complex in cyanosilylation reaction
  • Application of deprotonated phenyl bridged beta-ketimine lithium complex in cyanosilylation reaction
  • Application of deprotonated phenyl bridged beta-ketimine lithium complex in cyanosilylation reaction

Examples

Experimental program
Comparison scheme
Effect test

Synthetic example

[0027] o-Phenyl bridged β-ketoimine ligand (L ph h 2 )Synthesis

[0028]

[0029] Add 150 ml of absolute ethanol, 10.8 g of m-phenylenediamine (100 mmol), 20.5 mL of acetylacetone (200 mmol), and a catalytic amount of p-toluenesulfonic acid into a three-necked flask, heat and reflux for 24 hours to obtain a reddish-brown liquid and pale The yellow solid mixture was suction filtered, and the solid was recrystallized from absolute ethanol to obtain 24.5 g of light yellow needle-like crystals, with a yield of 90%, which was Ligand L ph h 2 . 1 H NMR (400 MHz, CDCl 3 ): δ12.47 (2H, s, N H ), 7.32-7.27 (1H, m, Ar H ), 6.94-6.91 (2H, m, Ar H ), 6.86 (1H, s, Ar H ), 5.21 (2H, s, C H =C(CH 3 )N), 2.10 (6H, s, C H 3 ), 2.01 (6H,s,C H 3 ). 13 C NMR (101 MHz, CDCl 3 ): δ 196.54 ( C OCH 3 ), 159.62 ( C =CH), 139.63(Ar C ), 129.71 (Ar C ), 121.45 (Ar C ), 120.43 (Ar C ), 98.20 (= C H), 29.25 ( C h 3),19.94 ( C h 3 ). HRMS (ESI-MS) calcd. for C 16 h 20 N 2...

Embodiment 1

[0039] Embodiment one: [L ph’ Li 4 (THF) 4 ] 2 Catalytic Reduction of Benzaldehyde and TMSCN

[0040] Under nitrogen atmosphere, add catalyst 0.6 mg (0.0005 mmol, 0.05%) to the reaction flask after dehydration and deoxygenation treatment, add benzaldehyde (101.6 μL, 1.0 mmol), TMSCN (137.6 μL, 1.1 mmol) with a pipette gun ), after reacting at room temperature for 15 min, use a dropper to draw a drop into the NMR tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ7.41-7.29 (m, 5H, Ar H ),5.42 (s, 1H, C H OSi(CH 3 ) 3 ), 0.15 (s, 9H, Si(C H 3 ) 3 ), see the map figure 1 .

Embodiment 2

[0041] Embodiment two: [L ph’ Li 4 (THF) 4 ] 2 Catalytic Reduction of p-Fluorobenzaldehyde and TMSCN

[0042] Under nitrogen atmosphere, add catalyst 0.6 mg (0.0005 mmol) to the reaction flask after dehydration and deoxygenation treatment, add p-fluorobenzaldehyde (107.2 μL, 1.0 mmol) and TMSCN (137.6 μL, 1.1 mmol) sequentially with a pipette gun , after reacting at room temperature for 15 min, use a dropper to draw a drop into the nuclear magnetic tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ7.48-7.44 (m, 2H, Ar H ), 7.12-7.08(m, 2H, Ar H ), 5.48 (s, 1H, C H OSi(CH 3 ) 3 ), 0.23 (s, 9H, Si(C H 3 ) 3 ).

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Abstract

The invention discloses application of a deprotonated phenyl bridged beta-ketimine lithium complex in a cyanosilylation reaction. In the complex, each beta-ketimine unit is a dianion, and the dianionbeta-ketimine group is a group with high activity, for example, the dianion beta-ketimine group can react with micromolecules containing active hydrogen and unsaturated bond organic micromolecules. Meanwhile, the complex can also be used as a precursor for further synthesizing the dianion beta-ketimine rare earth metal complex. The complex is applied to a cyanosilylation reaction of aldehyde, thereaction temperature is room temperature, and efficient reduction of aldehyde and TMSCN can be realized within a short reaction time.

Description

technical field [0001] The invention relates to a lithium complex and its application in the field of organic synthesis, in particular to a deprotonated β-ketimine lithium complex, its preparation method and its application in cyanidation of aldehydes. Background technique [0002] In organic chemistry, cyano silylation reaction is one of the most basic carbon-carbon bond formation reactions, and the resulting products are industrially valuable substrates and important intermediates because they can be further transformed into many useful Valuable organic compounds such as α-hydroxy acids, α-amino acids, β-amino alcohols, etc. [0003] In 1832, Winkler first reported the preparation of cyanohydrins by using HCN as a source of cyanide. However, due to the high toxicity of HCN and the difficulty in post-processing, a large number of less harmful and easy-to-control alternative cyanides appeared. Trimethylsilyl cyanide (TMSCN) is by far the most commonly used cyanation reagent...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07F7/18
CPCB01J31/2217C07F7/1804C07F7/188B01J2531/0241B01J2531/11B01J2231/342
Inventor 薛明强徐晓娟康子晗周帅陈素芳郑煜
Owner SUZHOU UNIV
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