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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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  • 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 used as starting materials, etc.
Especially for asymmetric carbonyl compounds, if the carbonyl compound has two α-carbons, there is also the problem of poor halogenation selectivity, which limits its application to a large extent.
Moreover, the reaction intermediates involved in the polarity inversion reaction usually cannot be separated, are unstable, and are sensitive to air and water vapor.

Method used

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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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preparation example Construction

[0030] One aspect of the embodiments of the present invention provides an effective synthesis method of an electrophilic polar enolate, comprising: using a monovalent silver salt as a catalyst to make terminal alkynyl compounds, pyridine or quinoline nitrogen oxides, or derivatives thereof Compounds and proton donors undergo addition reactions in organic solvents to obtain electrophilic enolates.

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

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

[0033] Various types of proton donors, such as HNTf 2 , MsOH, etc. are applicable to the enolate synthesis m...

Embodiment 1

[0041]

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

[0043] Add prefabricated compound A (1.1equiv., 0.828g), 1-undecyne (2mmol0.314g), silver trifluoromethanesulfonate (5%, 35.7mg), trifluoroethanol (4ml ), heated to 60° C., stirred and reacted for 12 hours, TLC monitoring was completed, and flash column chromatography (eluent dichloromethane:methanol=50:1) gave a reddish-brown oily liquid with a yield of 78%.

[0044] The characterization data of product 4 are as follows: 1 H NMR (CDCl 3 , 400MHz): δ8.86(dd, J=6.9,0.9Hz, 2H), 8.66(td, J=7.9,1.2Hz, 1H), 8.29(t, J=7.3Hz, 2H), 4.51(d, J=5.5Hz, 1H), 3.69(d, J=5.5Hz, 1H), 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 (...

Embodiment 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), trifluoroethanol 4ml, heated and stirred at 60°C for 12 hours, TLC monitoring was completed, and the flash 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): δ8.86(dd, J=6.9,0.9Hz, 2H), 8.29(t, J=7.3Hz, 2H), 4.51(d, J=5.5Hz, 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 ...

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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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