Preparation method and applications of a class of electrophilic enol salts

An enolate, electrophilic technology, applied in the field of metal organic catalysis, can solve the problems of instability, harsh reaction conditions, poor reaction selectivity, etc., and achieve the effects of diverse structures, high tolerance, and easy separation

Inactive Publication Date: 2017-09-15
XUZHOU MEDICAL UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

Although the polarity inversion method for carbonyl α-carbon has also been developed in recent years, it is mainly realized by using carbonyl α-carbon halide. However, these existing methods generally have expensive catalysts, harsh reaction conditions, and require anhydrous Oxygen-free conditions, poor reaction selectivity, many side reactions, and usually carbonyl compounds must be use

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  • Preparation method and applications of a class of electrophilic enol salts
  • Preparation method and applications of a class of electrophilic enol salts
  • Preparation method and applications of a class of electrophilic enol salts

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Example Embodiment

[0030] One aspect of the embodiments of the present invention provides an effective method for synthesizing electrophilic polar enol salts, which includes: using a monovalent silver salt as a catalyst to make terminal alkynyl compounds, pyridine or quinoline nitrogen oxides or their derivatives The compound and the proton donating agent undergo an addition reaction in an organic solvent to obtain an electrophilic enol salt.

[0031] Various types of terminal alkynyl compounds, such as terminal alkynes with different structures and different substituted functional groups, are applicable to the electrophilic enolate synthesis method of the present invention, and have wide versatility.

[0032] Various types of nitrogen oxides, such as pyridine, substituted pyridine nitrogen oxides, quinoline nitrogen oxides, etc., are applicable to the electrophilic enolate synthesis method of the present invention.

[0033] Many types of proton donors, such as HNTf 2 , MsOH, etc. are applicable to the...

Example Embodiment

[0040] Example 1

[0041]

[0042] Prefabricated compound A is a mixture of pyridine nitrogen oxide compound and acid. Under ice bath conditions, add pyridine nitrogen oxide (1.2equiv 0.456g) and Tf in a reaction flask containing 50ml of dichloromethane. 2 NH (1.1 equiv 1.232g), stirred at room temperature for 30 minutes, distilled off dichloromethane under reduced pressure to obtain a pale yellow oil.

[0043] Add pre-prepared compound A (1.1equiv., 0.828g), 1-undecyne (2mmol 0.314g), silver trifluoromethanesulfonate (5%, 35.7mg), trifluoroethanol (4ml ), heated to 60°C, stirred and reacted for 12 hours, TLC monitoring was completed, flash column chromatography (eluent dichloromethane: methanol = 50:1), a reddish brown oily liquid was obtained with a yield of 78%.

[0044] The characterization data of product 4 are as follows: 1 H NMR(CDCl 3 , 400MHz): δ 8.86 (dd, J = 6.9, 0.9 Hz, 2H), 8.66 (td, J = 7.9, 1.2 Hz, 1H), 8.29 (t, J = 7.3 Hz, 2H), 4.51 (d, J = 5.5Hz, 1H), 3.69 (d, J = 5...

Example Embodiment

[0045] Example 2

[0046]

[0047] In a 10ml reaction flask, add pyridine nitrogen oxide (1.2equiv, 0.261g), Tf 2 NH (1.1equiv, 0.616g), 1-undecyne (2mmol, 0.314g), silver acetate (5%, 33.4mg), 4ml trifluoroethanol, heated and stirred at 60℃ for 12 hours, TLC monitoring is complete, fast column Chromatography (eluent: dichloromethane: methanol = 50:1) gave the product as a reddish brown oily liquid with a yield of 84%.

[0048] The characterization data of the product are as follows: 1 H NMR(CDCl 3 , 400MHz): δ 8.86 (dd, J = 6.9, 0.9 Hz, 2H), 8.29 (t, J = 7.3 Hz, 2H), 4.51 (d, J = 5.5 Hz, 1H), 3.69 (d, J = 5.5Hz,1H),3.31(s,3H),2.38(t,J=7.5Hz,2H),1.76-1.50(m,2H),1.26(m,12H),0.87(t,J=6.9Hz, 3H); 13 C NMR(100MHz, CDCl 3 )δ166.22,146.70,141.98,130.31,88.93,67.04,31.76,30.90,29.33,29.17,29.09,28.82,26.42,22.58,14.01; 19 F NMR(CDCl 3 ,376MHz)δ-78.64; F 19 NMR(CDCl 3 ,376MHz)δ-78.78.IR(cm -1 ): 2947, 2846, 1667, 1482, 1350, 1185, 1135, 1055.ESI + calculated for[C 16 H 26 NO] + :278.2115,...

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Abstract

The invention relates to a preparation method and applications of a class of electrophilic enol salts, and belongs to the technical field of metal organic catalysis, wherein an alkynyl terminated compound, a nitrogen oxide and a proton supplying agent are subjected to an addition reaction in an organic solvent by using a silver salt as a catalyst to obtain the electrophilic enol salt, and the electrophilic enol salt is used for preparing a functionalized carbonyl compound. According to the present invention, with the synthesis method, by using various commercially availaboe monovalent silver salts as the catalyst and using various alkynyl terminated compounds as the starting raw material, the alkynyl terminated compound can be added by the protonated nitrogen oxide so as to achieve the synthesis of the special enol salt; the obtained enol salt has characteristics of diverse structure, high tolerance of the functional group, and good yield; and the electrophilic enol salts with the characteristic of easy separation is synthesized.

Description

technical field [0001] The invention specifically relates to a preparation method and application of a class of electrophilic enolate, and belongs to the technical field of organometallic catalysis. Background technique [0002] Electrophilic enolates have polarity-reversing properties. Polarity inversion was first proposed by American chemist E.J.Corey and German chemist D.Seebach. As an important synthetic strategy, it has been widely used in organic synthesis. Using this polarity inversion property can realize Synthesis of prepared substances. [0003] The polarity reversal examples of compounds reported in the literature are mainly for substrates such as aldehydes, ketones, imines, and halogenated hydrocarbons, and the polarity reversal is achieved by using metal reagents to interact with functional groups in these substrates. Due to the influence of the carbonyl group, the carbonyl α-carbon is partially negatively charged under normal circumstances and cannot interact...

Claims

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Application Information

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IPC IPC(8): C07D213/89C07C45/51C07C49/175C07C49/255C07C67/313C07C69/716C07D209/48C07C315/04C07C317/24
CPCC07C45/513C07C67/313C07C315/04C07D209/48C07D213/89C07C49/175C07C49/255C07C69/716C07C317/24
Inventor 徐洲翟荣良盛申归晓蝶梁婷李珂米佳佳
Owner XUZHOU MEDICAL UNIV
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