CN109096318B - Method for preparing organic boron compound and beta-hydroxy compound under catalysis of copper ion-loaded Y-type molecular sieve - Google Patents

Method for preparing organic boron compound and beta-hydroxy compound under catalysis of copper ion-loaded Y-type molecular sieve Download PDF

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CN109096318B
CN109096318B CN201810923555.1A CN201810923555A CN109096318B CN 109096318 B CN109096318 B CN 109096318B CN 201810923555 A CN201810923555 A CN 201810923555A CN 109096318 B CN109096318 B CN 109096318B
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李博解
朱磊
严沣
王伟
汪连生
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Abstract

The invention relates to a method for preparing an organic boron compound and a beta-hydroxyl compound by catalysis of a copper ion-loaded Y-type molecular sieve. Wherein the preparation of the organoboron compound mainly comprises the following steps: A. adding a copper ion loaded Y-type molecular sieve, tetrahydrofuran and water into a reaction container, and fully stirring at room temperature to obtain a mixed solution; B. adding an alpha, beta-unsaturated carbonyl compound and a pinacol diboron ester reagent into the mixed solution; C. stirring at room temperature for full reaction; D. and after the reaction is finished, separating and purifying to obtain the product. The method for preparing the beta-hydroxy compound comprises the steps of directly filtering after the step C, washing with tetrahydrofuran, combining a washing solution with a filtrate, adding sodium perborate tetrahydrate into the filtrate, stirring at room temperature for full reaction, separating and purifying to obtain the beta-hydroxy compound. The method has the beneficial effects that the Y-type molecular sieve loaded with copper ions is used as a catalyst for preparing the boron organic compound for the first time, no additional ligand is needed, and the method is high in catalytic efficiency, good in stability, non-toxic, green and environment-friendly.

Description

Method for preparing organic boron compound and beta-hydroxy compound under catalysis of copper ion-loaded Y-type molecular sieve
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing an organic boron compound and a beta-hydroxy compound by catalysis of a copper ion-loaded Y-type molecular sieve.
Background
The organic boron compound is an important intermediate, widely exists in the structures of natural products and drug molecules, and is also an important synthon for organic synthesis, and C-B bonds can be further converted into C-O, C-N bonds and C-C bonds. Compared with the traditional method using equivalent reaction reagents, the strategy of direct boron addition to unsaturated carbonyl compounds under the action of a catalyst is more direct and effective, and the method has attracted much attention in recent years. The catalysts used in the literature are mostly expensive transition metals, such as Rh, Ni, Pt, Pb, etc., which are expensive and not suitable for practical production. In addition, there is a method using monovalent copper in the literature, and although the reaction activity is improved, the operation process is complicated, and harsh conditions such as strong alkali (potassium tert-butoxide, etc.) and low temperature (-78 ℃) and strict absence of water are required, which greatly limits the application of the method in practical production. In contrast, bivalent copper is cheaper and more environmentally friendly, so that the development of a bivalent copper-based heterogeneous catalyst is currently a research focus and a difficulty in the field, and has important application value.
On the other hand, for heterogeneous catalysts, the choice of the support is of crucial importance, whereas molecular sieves derived from chitin deacetylation, which are widely available in nature, are undoubtedly very good choices. The molecular sieve is cheap and easy to obtain, and has excellent biocompatibility, safety, microbial degradability and the like. Up to now, there has been no report on the catalytic preparation of organoboron compounds using molecular sieves loaded with copper ions.
In addition, the conversion of the organoboron compound to the beta-hydroxy compound is an important application in industrial production, and because the beta-hydroxy structure widely exists in natural products and drug molecular structures, if a strategy of 'one-pot method' can be adopted, the boron addition of a substrate is firstly realized, and then the substrate is continuously converted into the beta-hydroxy compound without separation, so that the synthetic steps of the natural products are simplified, and the method has very important application value. In addition, the organoboron compounds are widely used in organic synthesis, and are also useful as initiators for polymerization reactions, kerosene antioxidants, bactericides, anticancer drugs, and the like.
Disclosure of Invention
The invention provides a method for preparing an organic boron compound and a beta-hydroxyl compound by using copper ion loaded Y-type molecular sieve microspheres, aiming at overcoming the following defects in the prior art to at least a certain extent: when noble metal is used as a catalyst for synthesizing the organic boron compound or an equivalent reagent is used as a synthesis raw material, the cost is high, and industrialization cannot be realized; when monovalent copper and nitrogen carbene ligand are used as catalysts, the operation process is complex, strong alkali (potassium tert-butoxide and the like) is needed, the temperature is low (-78 ℃), strict anhydrous and other harsh conditions are needed, and the production cost is high; when the existing beta-hydroxy compound is prepared by taking the organic boron compound as a starting point, the organic boron compound needs to be separated and purified from a reaction product after being synthesized, and continuous production is not carried out, so that the process route is complex and the production efficiency is low.
The technical scheme for solving the technical problems is as follows: the method for preparing the organic boron compound by the catalysis of the copper ion loaded Y-type molecular sieve comprises the following steps:
A. adding a copper ion-loaded Y-type molecular sieve, tetrahydrofuran and water into a reaction container, and fully stirring at room temperature to obtain a mixed solution, wherein the ratio of the amount of copper ion-loaded substances loaded by the copper ion-loaded Y-type molecular sieve to the amount of water is 0.002-0.003 mmol: 1mL, wherein the volume ratio of tetrahydrofuran to water is 0.5-1: 1;
B. adding an alpha, beta-unsaturated carbonyl compound I and pinacol diboron into the mixed solution obtained in the step A, wherein the ratio of the alpha, beta-unsaturated carbonyl compound I to the water in the mixed solution is 0.15-0.25 mmol: 1mL, the mass ratio of the pinacol diboron ester to the alpha, beta-unsaturated carbonyl compound I is 1.0-2.0: 1;
C. stirring and reacting at room temperature for 10-16 h;
D. after the reaction is finished, separating and purifying to obtain an organic boron compound II;
the chemical reaction equation is as follows:
Figure BDA0001764818840000031
wherein R is1Is a phenylketon group, a p-methylphenylketon group, a p-methoxyphenylketon group, a p-fluorophenylketon group, an acetyl group or a pivaloyl group; r2Is phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, m-bromophenyl, m-chlorophenyl, 2-thienyl, 2-naphthyl or 3-propenylphenyl.
On the basis of the technical scheme, the invention can further specifically select the following.
Specifically, the loading capacity of the copper ions in the Y-type molecular sieve loading the copper ions in the A is 5-10 wt%. The preparation method of the copper ion loaded Y-type molecular sieve is the prior art and can be carried out in the literature reference, for example, the following method can be adopted for preparation: (1) preparing a copper sulfate solution with the concentration of 1 mol/L. (2) Weighing 10gY molecular sieve (Na type), adding into a beaker, adding 200mL copper sulfate solution, stirring for five minutes, mixing uniformly, starting heating, and reacting for 8h when the temperature rises to 80 ℃. (3) The hot filtration was then continued and 200mL of copper sulfate solution was added to the solid and the procedure of (2) was repeated. (4) The turbid solution is filtered, and the solid is washed by water for a plurality of times until the filtrate is detected to be free of Cu (II) ions. (5) The blue solid was dried at 80 ℃ for 12 h. (6) And (3) heating the dried solid sample to 500 ℃ by a program (1 ℃/min) under the condition of introducing nitrogen, keeping the temperature for 3h, taking out the sample after the temperature is reduced to room temperature, and always using nitrogen for protection in the whole process. Finally obtaining the Y-type molecular sieve (Y-zeolite @ Cu (II)) loading the copper ions. The cupric salt is at least one of cupric hydroxide, cupric oxide, copper cyanide, cupric sulfate, cupric chloride, cupric fluoride, cupric bromide and cupric carbonate hydroxide. Copper sulfate is preferably used.
Specifically, in the step A, the loading amount of copper ions in the copper ion-loaded Y-type molecular sieve is 5-10 wt%
Specifically, the reaction temperature in the step C is 0-30 ℃. Preferably, the temperature is 20 to 25 ℃.
Preferably, the ratio of the amount of pinacol diborate reagent to α, β -unsaturated carbonyl compound I in B is 1.2: 1.
specifically, the specific steps of separating and purifying in D are as follows: after the reaction is finished, filtering and washing with ethyl acetate, extracting with ethyl acetate, separating out an organic phase, drying with anhydrous sodium sulfate, filtering, removing the solvent by rotary evaporation, and separating and purifying the residue by using a mixed solvent column chromatography of ethyl acetate and petroleum ether to obtain the compound.
The invention also provides a method for preparing a beta-hydroxy compound by catalyzing the copper ion loaded Y-type molecular sieve, which comprises the following steps:
A. adding a copper ion-loaded Y-type molecular sieve, tetrahydrofuran and water into a reaction container, and fully stirring at room temperature to obtain a mixed solution, wherein the dosage ratio of copper ions loaded by the copper ion-loaded Y-type molecular sieve to water is 0.01-0.015 mmol: 1mL, wherein the volume ratio of tetrahydrofuran to water is 0.5-1: 1;
B. adding an alpha, beta-unsaturated carbonyl compound I and pinacol diboron into the mixed solution obtained in the step A, wherein the ratio of the alpha, beta-unsaturated carbonyl compound I to the water in the mixed solution is 0.15-0.25 mmol: 1mL, the ratio of the amount of pinacol diboron to the amount of the alpha, beta-unsaturated carbonyl compound I is 1.0-2.0: 1;
C. stirring and reacting at room temperature for 10-16 h to obtain reaction liquid containing the organic boron compound II;
D. after the reaction is finished, filtering the reaction liquid, washing a filter cake with tetrahydrofuran, combining a washing liquid with the filtrate, adding sodium perborate tetrahydrate into the combined filtrate, stirring and reacting for 4-8 h at room temperature, wherein the ratio of the sodium perborate tetrahydrate to the amount of the alpha, beta-unsaturated carbonyl compound I added in the step B is 2.0-4.0: 1, the volume ratio of tetrahydrofuran used for washing in the step D to water added in the step A is 1.5-2: 1;
E. after the reaction is finished, separating and purifying to obtain a beta-hydroxy compound III;
the chemical reaction equation is as follows:
Figure BDA0001764818840000051
wherein R is1Is phenyl ketone group, p-methyl phenyl ketone group, p-methoxy phenyl ketone group, p-fluoro phenyl ketone group, acetyl group and pivaloyl group; r2Is phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, m-bromophenyl, m-chlorophenyl, 2-thienyl, 2-naphthyl, 3-propenylphenyl.
On the basis of the technical scheme, the invention can further specifically select the following.
Specifically, the loading capacity of the copper ions in the Y-type molecular sieve loading the copper ions in the A is 5-10 wt%.
Specifically, the reaction temperature in the step C is 0-30 ℃. Preferably, the temperature is 20 to 25 ℃.
Preferably, the ratio of the amount of pinacol diborate reagent to α, β -unsaturated carbonyl compound I in B is 1.2: 1.
specifically, the ratio of the amount of the sodium perborate tetrahydrate added in D to the amount of the α, β -unsaturated carbonyl compound (I) added in B is 2.0 to 4.0: 1, the volume ratio of tetrahydrofuran used for washing in the step D to water added in the step A is 1.5-2: 1.
specifically, the separation and purification steps in E are as follows: after the reaction is finished, filtering and washing with ethyl acetate, extracting with ethyl acetate, separating out an organic phase, drying with anhydrous sodium sulfate, filtering, removing the solvent by rotary evaporation, and separating and purifying the residue by using a mixed solvent column chromatography of ethyl acetate and petroleum ether to obtain the compound.
Compared with the prior art, the invention has the beneficial effects that:
1. the method provided by the invention uses the Y-type molecular sieve loaded with copper ions as the catalyst for preparing the boron organic compound for the first time, and not only is the carrier framework but also the ligand of the copper ions, and compared with the traditional adsorption load, the method has the advantages that the combination of the copper ions and the carrier framework is more stable, and meanwhile, no additional ligand with complex structure is required to be added, so that the method is high in catalytic efficiency, good in stability, free of toxicity, good in biocompatibility and environment-friendly;
2. compared with the similar reaction in the prior art, the catalyst dosage and the reaction time of the method are greatly reduced, and the higher conversion rate of reactants can be realized only by using lower catalyst dosage;
3. the method has mild reaction conditions, can carry out reaction at room temperature, does not need an anhydrous and oxygen-free reaction environment, and is simple, convenient and easy to operate;
4. the method has wide application, can be used for boron addition of various different types of alpha, beta-unsaturated carbonyl compounds, and successfully prepares corresponding organic boron compounds and beta-hydroxyl compounds.
5. The method can adopt a one-pot method strategy, and the beta-hydroxy compound containing carbonyl can be directly prepared from the starting raw materials through continuous boron addition reaction and oxidation reaction.
6. The molecular sieve catalytic material used in the method can be recycled, the catalytic material can be reused for more than 7 times, the reaction activity cannot be obviously reduced, the separation of the catalytic material can be realized by simple filtering operation, and the method is more suitable for industrial large-scale production.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to specific examples, which are only used for explaining the present invention and are not used for limiting the scope of the present invention.
The initial raw material is alpha, beta-unsaturated carbonyl compound I, and the organoboron compound II is prepared by the method provided by the invention and then is converted into beta-hydroxy compound III.
Examples below the conversion of alpha, beta-unsaturated carbonyl Compounds IHas the formula of
Figure BDA0001764818840000061
Wherein R is1Is phenyl ketone group, p-methyl phenyl ketone group, p-methoxy phenyl ketone group, p-fluoro phenyl ketone group, acetyl group, pivaloyl group, cyano group, m-methyl phenyl ketone group; r2Is phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, m-bromophenyl, m-chlorophenyl, 2-thienyl, 2-naphthyl, 3-propenylphenyl.
In the following examples, R of the preferred, α, β -unsaturated carbonyl compounds I-11Is a phenylketonyl group, R2Is phenyl; r of I-21Is a phenylketonyl group, R2Is p-methylphenyl; r of I-31Is a phenylketonyl group, R2Is p-methoxyphenyl; r of I-41Is a para-methylphenonyl radical, R2Is phenyl; r of I-51Is p-methoxybenzophenone radical, R2Is phenyl; r of I-61Is p-fluorophenonyl radical, R2Is phenyl; r of I-71Is a phenylketo group, R2Is p-fluorophenyl; r of I-81Is a phenylketonyl group, R2Is p-chlorophenyl; r of I-91Is a phenylketo group, R2Is p-bromophenyl; r of I-101Is acetyl, R2Is phenyl; r of I-111Is pivaloyl, R2Is phenyl; r of I-121Is a phenylketonyl group, R2Is 2-thienyl; r of I-131Is p-fluorophenonyl radical, R2Is 2-thienyl; r of I-141Is a phenylketonyl group, R2Is p-trifluoromethylphenyl; r of I-151Is p-methoxyphenonyl, R2Is p-methoxyphenyl; r of I-161Is a para-methylphenonyl radical, R2Is p-fluorophenyl; r of I-171Is a para-methylphenonyl radical, R2Is p-bromophenyl; r of I-181Is p-fluorophenonyl radical, R2Is p-bromophenyl; r of I-191Is an ortho-methylbenzonyl radical, R2Is phenyl; r of I-201Is p-methoxyphenonyl, R2Is a chlorophenyl group; r of I-211Is a phenylketonyl group, R2Is 2-naphthyl; r of I-221Is acetyl, R2Is p-methoxyphenyl; r of I-231Is a phenylketo group, R2Is 3-propenyl phenyl.
In the following examples, organoboron compounds II correspond in turn to the following chemical structures:
Figure BDA0001764818840000071
the chemical structural formula of the beta-hydroxy compound III in the following examples corresponds to the following:
Figure BDA0001764818840000072
Figure BDA0001764818840000081
the methods used in the following examples are conventional in the art and the pharmaceutical products used are commercially available products unless otherwise specified.
Example 1:
a process for producing an organoboron compound II-1, which comprises the steps of:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol (a supporting amount of 5 to 10 wt% based on the amount of the supported copper ion species, the same applies hereinafter), and 1.0mL of tetrahydrofuran and 1.0mL of water were added and stirred at room temperature (20 to 25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-1(41.6mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separatedUsing anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 9:1 to give II-1 as a pale yellow solid, 65.2mg, 97% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)8.00–7.93(m,2H),7.52(t,J＝7.5Hz, 1H),7.41(t,J＝7.8Hz,2H),7.32–7.23(m,4H),7.16-7.12(m,1H),3.54-3.51(m, 1H),3.41-3.38(m,1H),1.26(s,6H),1.18(s,6H).
13C NMR(100MHz,Chloroform-d)＝202.4,144.6,139.4,135.6,131.2, 131.1,131.0,130.7,128.3,86.1,46.0,27.2,27.1.
11B NMR(120MHz,Chloroform-d)32.6(s).
example 2:
a process for producing an organoboron compound II-2, which comprises the steps of:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-2(47.7mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 9:1 to give II-2 as a pale yellow solid, 72.5mg, in 99% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)8.00–7.92(m,2H),7.57–7.36(m,3H), 7.21(d,J＝8.5Hz,2H),6.83(d,J＝8.6Hz,2H),3.76(s,3H),3.51-3.45(m,1H), 3.39-3.35(m,1H),2.74-2.70(m,1H),1.20-1.15(m,12H).
13C NMR(100MHz,Chloroform-d)＝199.8,157.6,136.8,133.8,132.8, 129.3,128.5,128.0,113.9,83.3,55.2,43.6,24.6,24.5.
11B NMR(120MHz,Chloroform-d)32.9(s).
example 3:
a process for producing an organoboron compound II-3, which comprises the steps of:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-3(45.3mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 9:1 to give II-369.4 mg in 98% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)8.03–7.85(m,2H),7.53(t,J＝7.5Hz, 1H),7.42(t,J＝7.8Hz,2H),7.31–7.20(m,2H),6.94(t,J＝8.8Hz,2H), 3.50-3.45(m,1H),3.40-3.36(m,1H),2.78-2.74(m,1H),1.23(s,6H),1.16(s, 6H)
13C NMR(100MHz,Chloroform-d)199.5,161.9,160.3,137.6,137.5, 136.7,133.0,129.7,129.7,128.5,128.0,115.3,115.1,83.5,43.2,24.6,24.5.
11B NMR(120MHz,Chloroform-d)33.3(s).
example 4:
a preparation method of a beta-hydroxy compound III-1 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-1(41.7mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-1 as a colorless oily liquid, 43.9mg, in 97% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.97(d,J＝7.2Hz,2H),7.61-7.57(m,1H), 7.49-7.44(m,4H),7.41(t,J＝7.5Hz,2H),7.33-7.29(m,1H),5.37(t,J＝6.1Hz, 1H),3.65(br,1H),3.39-3.37(m,2H).
13C NMR(100MHz)；＝200.1,142.9,136.4,133.6,133.6,128.7,128.5, 128.1,127.6,125.7,70.0,47.3.
example 5:
a preparation method of a beta-hydroxy compound III-2 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL tetrahydrofuran was addedAnd 1.0mL of water, stirred at room temperature (20-25 ℃ C., same as below) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-2(47.7mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-2 as a white solid, 45.2mg, 94% yield.
The nuclear hydrogen spectrum and carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.97(d,J＝7.0Hz,2H),7.61-7.57(m,1H),7.49(t, J＝7.7Hz,2H),7.21(d,J＝7.9Hz,2H),5.34-5.30(m,1H),3.60(s,1H), 3.43-3.32(m,2H),2.37(s,3H).
magnetic field
13C NMR(100MHz)；＝200.1,140.0,137.3,136.5,133.5,129.2,128.6, 128.1,125.6,77.3,77.0,76.7,69.8,47.3,21.1.
Example 6:
a preparation method of a beta-hydroxy compound III-3 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-3(45.3mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-3 as a colorless oily liquid, 42.5mg, 83% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.97-7.94(m,2H),7.61-7.57(m,1H),7.49-7.45 (m,2H),7.38-7.35(m,2H),6.92-6.90(m,2H),5.31(dd,J＝7.6,4.6Hz,1H), 3.81(s,1H),3.38-3.35(m,2H).
13C NMR(100MHz)；＝200.3,159.1,136.6,135.1,133.6,128.7,128.1, 127.0,113.9,77.3,77.0,76.7,69.7,55.3,47.3.
example 7:
a preparation method of a beta-hydroxy compound III-4 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-4(44.5mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-4 as a white solid, 43.3mg, 90% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.84(d,J＝8.3Hz,2H),7.42(d,J＝7.2Hz,2H), 7.37(t,J＝7.4Hz,2H),7.30(d,J＝7.2Hz,1H),7.26-7.23(m,2H),5.33-5.30 (m,1H),3.71(s,1H),3.36-3.27(m,2H),2.39(s,3H).
13C NMR(100MHz)；＝199.8,144.6,142.9,134.0,129.3,128.5,128.2, 127.6,125.7,77.3,77.0,76.7,70.0,47.2,21.7.
example 8:
a preparation method of a beta-hydroxy compound III-5 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-5(47.7mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, and then with ethyl acetate (3 in a recovery section)10mL), and after separating the organic phase, using anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-5 as a white solid, 44.1mg, 86% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.95(d,J＝8.8Hz,2H),7.45(d,J＝6.7Hz,2H), 7.40(t,J＝7.3Hz,2H),7.32(t,J＝7.2Hz,1H),6.94(d,J＝8.8Hz,2H),5.34 (dd,J＝8.3,3.8Hz,1H),3.87(s,3H),3.79(s,1H),3.36-3.26(m,2H).
13C NMR(100MHz)；＝198.8,163.9,143.0,130.5,129.6,128.5,127.6, 125.7,113.8,77.3,77.0,76.7,70.1,55.5,46.9.
example 9:
a preparation method of a beta-hydroxy compound III-6 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) Calculated as Cu ion 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, and stirred at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-6(45.3mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-6 colorless oily liquid, 41.0mg, yield 84%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝8.00(dd,J＝8.9Hz,5.4Hz,2H),7.44(d,J＝6.8 Hz,2H),7.40(t,J＝7.4Hz,2H),7.32(t,J＝7.1Hz,1H),7.15(t,J＝8.6Hz,2H), 5.36(dd,J＝8.6,3.6Hz,1H),3.55(s,1H),3.40-3.28(m,2H).
13C NMR(100MHz)；＝198.4,167.3,164.7,142.8,132.99,132.96,130.9, 130.8,128.6,127.7,125.7,115.9,115.7,77.3,77.0,76.7,70.0,47.3.
example 10:
a preparation method of a beta-hydroxy compound III-7 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-7(44.5mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-7 as a colorless oily liquid, 45.4mg, yield 93%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.96-7.94(m,2H),7.61-7.57(m,1H),7.49-7.39 (m,5H),7.08(t,J＝8.7Hz,1H),5.34(t,J＝6.1Hz,1H),3.72(br,1H),3.35(d, J＝6.1Hz,2H).
13C NMR(100MHz)；＝200.0,163.4,160.9,138.7,138.6,136.4,133.7, 128.7,128.1,127.44,127.36,115.4,115.2,69.4,47.3.
example 11:
a preparation method of a beta-hydroxy compound III-8 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-8(48.5mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-8 white solid, 43.8mg, yield 84%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.96(d,J＝6.9Hz,2H),7.62(t,J＝7.4Hz,1H), 7.50(t,J＝7.7Hz,2H),7.39-7.34(m,4H),5.34(dd,J＝7.8,4.3Hz,1H),3.66(s, 1H),3.35-3.33(m,2H).
13C NMR(100MHz)；＝200.0,141.4,136.4,133.8,133.3,128.74,128.68, 128.1,127.1,77.3,77.0,76.7,69.4,47.2.
example 12:
a preparation method of a beta-hydroxy compound III-9 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4)
0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added and stirred at room temperature (20-25 ℃ C., the same applies to the lower phase) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-9(57.4mg, 0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-9 as a white solid, 40.9mg, 67% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.95(d,J＝7.0Hz,2H),7.62(t,J＝7.4Hz,1H), 7.51-7.45(m,4H),7.33(d,J＝8.4Hz,2H),5.32(dd,J＝7.4,4.8Hz,1H),3.68 (s,1H),3.38-3.28(m,2H).
13C NMR(100MHz)；＝199.9,141.9,136.3,133.8,131.6,128.7,128.1, 127.5,121.4,77.3,77.0,76.6,69.4,47.2.
example 13:
a preparation method of a beta-hydroxy compound III-10 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-10(29.2 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-10 pale yellow oily liquid, 26.9mg, yield 82%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.36(d,J＝4.5Hz,4H),7.30-7.27(m,1H), 5.17-5.13(m,1H),3.39(s,1H),2.93-2.79(m,2H),2.79(s,3H).
13C NMR(100MHz)；＝209.1,142.7,128.5,127.6,125.6,77.3,77.0,76.7, 69.8,51.9,30.7.
example 14:
a preparation method of a beta-hydroxy compound III-11 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-11(37.7 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-11 as a pale yellow oily liquid, 29.3mg, in 71% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.38-7.28(m,5H),5.15-5.11(m,1H),3.64(s,1H), 2.89-2.87(m,2H),1.13(s,9H).
13C NMR(100MHz)；＝216.8,143.0,128.4,127.5,125.6,77.3,77.0,76.7, 70.0,45.4,44.3,26.1,30.7.
example 15:
a method for preparing a beta-hydroxy compound III-12, which comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-12(42.9 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 column to give III-12 as a colorless oily liquid, 37.2mg, yield 80%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.97(d,J＝8.1Hz,2H),7.61-7.57(m,1H), 7.49-7.45(m,2H),7.26-7.25(m,1H),7.03-6.97(m,2H),5.61-5.57(m,1H),3.83 (s,1H),3.51-3.48(m,2H).
13C NMR(100MHz)；＝199.5,146.6,136.3,133.7,128.7,128.1,126.6, 124.6,123.5,77.3,70.0,76.7,66.4,47.1.
example 16:
a preparation method of a beta-hydroxy compound III-13 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-13(46.5 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was passed through ethyl acetate/stoneColumn chromatography purification of 4:1 mixed solvent with oil and ether gave III-13 as a pale yellow oily liquid, 34.5mg, 69% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝8.01-7.98(m,2H),7.28-7.26(m,1H),7.17(t,J＝ 8.6Hz,2H),7.04-6.98(m,2H),5.61-5.58(m,1H),3.75(s,1H),3.54-3.41(m, 2H).
13C NMR(100MHz)；＝197.8,167.3,164.8,146.6,132.90,132.87,130.9, 130.8,126.7,124.7,123.5,115.9,115.7,77.3,77.0,76.7,66.3,47.1.
example 17:
a method for preparing a beta-hydroxy compound III-14, which comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-14(55.3 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-14 as a colorless oily liquid, 32.9mg, in 56% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.96(d,J＝7.0Hz,2H),7.65-7.55(m,5H),7.50(t, J＝7.8Hz,2H),7.49(t,J＝7.7Hz,2H),5.43(dd,J＝8.1,5.4Hz,1H),3.79(s, 1H),3.41-3.31(m,2H).
13C NMR(100MHz)；＝199.8,146.9,136.3,133.9,130.3,130.0,129.6, 129.3,128.8,128.1,126.0,125.53,125.50,125.46,125.42,122.7,77.3,77.0, 76.7,47.2.
example 18:
a preparation method of a beta-hydroxy compound III-15 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added and stirred at room temperature (20-25 ℃ C., the same applies to the lower phase) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-15(53.7 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-15 white solid, 57.3mg, yield>99％。
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.95(d,J＝8.8Hz,2H),7.37(d,J＝8.6Hz,2H), 6.94(t,J＝8.2Hz,4H),5.29-5.26(m,1H),3.87(s,3H),3.81(s,3H),3.72(s, 1H),3.34-3.25(m,2H).
13C NMR(100MHz)；＝198.9,163.9,159.0,135.2,130.5,129.6,127.0, 113.9,113.8,77.3,77.0,76.7,69.8,55.5,55.3,46.8.
example 19:
a preparation method of a beta-hydroxy compound III-16 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-16(48.1 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-16 as a white solid, 43.9mg, 85% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.86(d,J＝8.3Hz,2H),7.42-7.39(m,2H),7.27 (d,J＝8.0Hz,2H),7.08(t,J＝8.7Hz,2H),5.33-5.29(m,1H),3.77(s,1H), 3.32-3.25(m,1H),2.42(s,3H).
13C NMR(100MHz)；＝199.7,163.4,160.9,144.7,138.74,138.71,134.0, 129.4,128.2,127.44,127.36,115.4,115.2,77.3,77.0,76.7,69.5,47.1,21.7.
example 20:
a preparation method of a beta-hydroxy compound III-17 comprises the following steps:
A. in 2.5mLAdding a Y-type molecular sieve (Y-Zeolite @ CuSO) loaded with copper ions into a reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-17(63.4 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-17 white solid, 30.8mg, yield 46%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.92(d,J＝8.9Hz,2H),7.50(d,J＝8.4Hz,2H), 7.32-7.30(m,2H),6.94(d,J＝8.9Hz,2H),5.29-5.26(m,1H),3.874(br,1H), 3.867(s,3H),3.32-3.25(m,2H).
13C NMR(100MHz)；＝198.5,164.0,142.0,131.5,130.5,129.4,127.5, 121.3,113.9,69.5,55.5,46.7.
example 21:
a method for preparing a beta-hydroxy compound III-18, which comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, the alpha, beta-unsaturated carbonylation is continuously and sequentially addedCompound I-18(61.0 mg,0.2mmol) and pinacol diboron (B)2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-18 as a pale yellow solid, 37.5mg, 58% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.99(dd,J＝8.9Hz,5.4Hz,2H),7.51(d,J＝8.4 Hz,1H),7.32(d,J＝8.4Hz,2H),7.16(t,J＝8.6Hz,2H),5.32-5.28(m,1H), 3.59(s,1H),3.29(s,1H).
13C NMR(100MHz)；＝198.2,167.4,164.8,141.8,132.83,132.80,131.7, 130.9,130.8,127.4,1215,116.0,115.8,77.3,77.2,77.0,76.7,69.4,47.1.
example 22:
a method for preparing a beta-hydroxy compound III-19, comprising the steps of:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-19(61.0 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using an ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give III-19 as a white solid, 41.3mg, yield 86%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.77-7.74(m,2H),7.46-7.44(m,2H),7.41-7.35 (m,4H),7.33-7.29(m,1H),5.36(dd,J＝7.0,5.1Hz,1H),3.64(s,1H), 3.37-3.36(m,2H),2.41(s,3H).
13C NMR(100MHz)；＝200.4,142.9,138.5,136.6,134.4,128.7,128.6, 128.5,127.6,125.7,125.4,77.3,77.0,76.7,70.0,47.4,21.3.
example 23:
a preparation method of a beta-hydroxy compound III-20 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4)
0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added and stirred at room temperature (20-25 ℃ C., the same applies to the lower phase) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-20(61.0 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-20 as a white solid, 54.7mg, 94% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.95(d,J＝8.9Hz,2H),7.7.-7.70(m,1H), 7.35-7.31(m,2H),7.25-7.20(m,1H),6.93(d,J＝9.0Hz,2H),5.67-5.61(m, 1H),4.07(br,1H),3.86(s,3H),3.54-3.49(m,1H),3.11-3.04(m,1H).
13C NMR(100MHz)；＝198.8,163.9,140.4,131.1,130.5,129.4,129.2, 128.5,127.23,127.18,113.8,66.9,55.5,44.8.
example 24:
a preparation method of a beta-hydroxy compound III-21 comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4)
0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added and stirred at room temperature (20-25 ℃ C., the same applies to the lower phase) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-21(61.0 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering, and rotatingThe solvent was removed by evaporation. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-21 as a white solid, 45.3mg, 82% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝8.07-8.05(m,1H),8.00-7.90(m,3H),7.83-7.81 (m,2H),7.59-7.43(m,6H),6.18(dd,J＝9.0,2.6Hz,1H),3.83(br,1H), 3.58-3.49(m,2H).
13C NMR(100MHz)；＝200.2,138.4,136.4,133.7,133.6,129.8,129.0, 128.6,128.1,128.0,126.2,125.6,125.5,123.1,122.7,66.7,46.7.
example 25:
a method for preparing a beta-hydroxy compound III-22, which comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, an α, β -unsaturated carbonyl compound I-22(61.0 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-22 as a white solid, 31.9mg, in 82% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.29-7.26(m,2H),6.89(d,J＝8.7Hz,2H), 5.12-5.08(m,1H),3.80(s,3H),3.23(s,1H),2.89-2.76(m,2H),2.19(s,3H).
13C NMR(100MHz)；＝209.2,159.1,134.8 126.9,113.9,77.3,77.0,76.7, 69.5,55.3,51.9,30.8.
example 26:
a method for preparing a beta-hydroxy compound III-23, which comprises the following steps:
A. a copper ion-loaded Y-type molecular sieve (Y-Zeolite @ CuSO) was added to a 2.5mL reaction tube4) 0.002mmol, and 1.0mL of tetrahydrofuran and 1.0mL of water were added, followed by stirring at room temperature (20-25 ℃ C., the same applies hereinafter) for 1 hour;
B. to the above system, α, β -unsaturated carbonyl compound I-23(61.0 mg,0.2mmol) and pinacol ester diboron (B) were added successively2(pin)2)(60.9mg,2.4mmol)；
C. The whole reaction system is stirred and reacted at room temperature, and the reaction time is 12 hours;
D. after the reaction, the whole reaction system was filtered, and after the reaction was completed, the whole reaction system was filtered and washed with 2mL of tetrahydrofuran. To the residue was directly added 244mg of sodium perborate tetrahydrate, and the whole was stirred at room temperature for 4 hours.
E. After completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether (4: 1) to give III-23 as a white solid, 15.1mg, 30% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz)；＝7.91-7.88(m,2H),7.54-7.50(m,1H),7.42-7.38 (m,2H),7.33-7.31(m,2H),7.26-7.22(m,2H),7.18-7.15(m,1H),6.65-6.61(m, 1H),6.27(dd,J＝15.9Hz,6.0Hz,1H),4.89-4.86(m,1H),3.38(s,1H), 3.26-3.16(m,2H).
13C NMR(100MHz)；＝200.3,136.54,136.51,133.6,130.4,130.2,128.7, 128.5,128.1,127.7,126.5,77.3,77.0,76.7,68.6,45.2.
from the above embodiments, it can be seen that the method for preparing organoboron compounds and β -hydroxy compounds provided by the present invention has the characteristics of fast reaction rate, high yield, mild reaction conditions, simple process, etc.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A method for preparing an organic boron compound by catalysis of a copper ion-loaded Y-type molecular sieve is characterized by comprising the following steps:
A. adding a copper ion-loaded Y-type molecular sieve, tetrahydrofuran and water into a reaction container, and fully stirring at room temperature to obtain a mixed solution, wherein the ratio of the amount of copper ion-loaded substances loaded by the copper ion-loaded Y-type molecular sieve to the amount of water is 0.002-0.003 mmol: 1mL, wherein the volume ratio of tetrahydrofuran to water is 0.5-1: 1;
B. adding an alpha, beta-unsaturated carbonyl compound I and pinacol diboron into the mixed solution obtained in the step A, wherein the ratio of the alpha, beta-unsaturated carbonyl compound I to the water in the mixed solution is 0.15-0.25 mmol: 1mL, the ratio of the amount of pinacol diboron to the amount of the alpha, beta-unsaturated carbonyl compound I is 1.0-2.0: 1;
C. stirring and reacting at room temperature for 10-16 h;
D. after the reaction is finished, separating and purifying to obtain an organic boron compound II;
the chemical reaction equation is as follows:
Figure FDA0002685826380000011
wherein R is1Is a phenylketon group, a p-methylphenylketon group, a p-methoxyphenylketon group, a p-fluorophenylketon group, an acetyl group or a pivaloyl group; r2Is phenyl, p-methylphenylP-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, m-bromophenyl, m-chlorophenyl, 2-thienyl, 2-naphthyl or styryl.
2. The method for preparing the organoboron compound by catalyzing the copper ion-loaded Y-type molecular sieve as claimed in claim 1, wherein: in the step A, the loading amount of copper ions in the copper ion-loaded Y-type molecular sieve is 5-10 wt%.
3. The method for preparing the organoboron compound by catalyzing the copper ion-loaded Y-type molecular sieve as claimed in claim 1, wherein: in step B, the mass ratio of pinacol diboron to α, β -unsaturated carbonyl compound I is 1.2: 1.
4. a method for preparing organoboron compound catalyzed by the copper ion-loaded Y-type molecular sieve as claimed in any one of claims 1 to 3, characterized in that: the specific steps of separation and purification in the step D are as follows: and after the reaction is finished, filtering the reaction liquid, washing a filter cake by using ethyl acetate, combining the filtrate with a washing liquid, extracting the filtrate by using ethyl acetate, separating an organic phase, drying the organic phase by using anhydrous sodium sulfate, filtering, removing the solvent in the filtrate by rotary evaporation, and separating and purifying the residue by using a mixed solvent column chromatography of the ethyl acetate and petroleum ether to obtain the compound.
5. A method for preparing a beta-hydroxy compound by catalysis of a copper ion-loaded Y-type molecular sieve is characterized by comprising the following steps:
A. adding a copper ion-loaded Y-type molecular sieve, tetrahydrofuran and water into a reaction container, and fully stirring at room temperature to obtain a mixed solution, wherein the dosage ratio of copper ions loaded by the copper ion-loaded Y-type molecular sieve to water is 0.01-0.015 mmol: 1mL, wherein the volume ratio of tetrahydrofuran to water is 0.5-1: 1;
B. adding an alpha, beta-unsaturated carbonyl compound I and pinacol diboron into the mixed solution obtained in the step A, wherein the dosage ratio of the alpha, beta-unsaturated carbonyl compound I to water in the mixed solution is 0.15-0.25 mmol: 1mL, the ratio of the amount of pinacol diboron to the amount of the alpha, beta-unsaturated carbonyl compound I is 1.0-2.0: 1;
C. stirring and reacting at room temperature for 10-16 h to obtain reaction liquid containing the organic boron compound II;
D. after the reaction is finished, filtering the reaction liquid, washing a filter cake with tetrahydrofuran, combining a washing liquid with the filtrate, adding sodium perborate tetrahydrate into the combined filtrate, stirring and reacting for 4-8 h at room temperature, wherein the ratio of the sodium perborate tetrahydrate to the amount of the alpha, beta-unsaturated carbonyl compound I added in the step B is 2.0-4.0: 1, the volume ratio of tetrahydrofuran used for washing in the step D to water added in the step A is 1.5-2: 1;
E. after the reaction is finished, separating and purifying to obtain a beta-hydroxy compound III;
the chemical reaction equation is as follows:
Figure FDA0002685826380000031
wherein R is1Is a phenylketon group, a p-methylphenylketon group, a p-methoxyphenylketon group, a p-fluorophenylketon group, an acetyl group or a pivaloyl group; r2Is phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, m-bromophenyl, m-chlorophenyl, 2-thienyl, 2-naphthyl, styryl.
6. The method for preparing beta-hydroxy compound by catalysis of the copper ion-loaded Y-type molecular sieve according to claim 5, wherein the method comprises the following steps: in the step A, the loading amount of copper ions in the copper ion-loaded Y-type molecular sieve is 5-10 wt%.
7. The method for preparing the beta-hydroxy compound by catalyzing the copper ion loaded Y-type molecular sieve according to claim 5, is characterized in that: in step B, the mass ratio of pinacol diboron to α, β -unsaturated carbonyl compound I is 1.2: 1.
8. the method for preparing beta-hydroxy compound by catalysis of the copper ion-loaded Y-type molecular sieve according to any one of claims 5 to 7, wherein: the specific steps of separation and purification in the step E are as follows: and after the reaction is finished, filtering, washing a filter cake by using ethyl acetate, combining the filtrate with a washing solution, extracting the filtrate by using ethyl acetate, separating an organic phase, drying the organic phase by using anhydrous sodium sulfate, filtering, removing the solvent in the filtrate by rotary evaporation, and separating and purifying the residue by using a mixed solvent column chromatography of the ethyl acetate and petroleum ether to obtain the compound.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110054170A1 (en) * 2009-08-31 2011-03-03 Florida State University Research Foundation Six-membered N-Heterocyclic Carbene-based catalysts for asymmetric reactions
CN106892935A (en) * 2016-04-27 2017-06-27 湖北工程学院 A kind of immobilized copper catalysis of shitosan prepare method and the application of organoboron compound
CN107573370A (en) * 2017-09-19 2018-01-12 湖北工程学院 The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110054170A1 (en) * 2009-08-31 2011-03-03 Florida State University Research Foundation Six-membered N-Heterocyclic Carbene-based catalysts for asymmetric reactions
CN106892935A (en) * 2016-04-27 2017-06-27 湖北工程学院 A kind of immobilized copper catalysis of shitosan prepare method and the application of organoboron compound
CN107573370A (en) * 2017-09-19 2018-01-12 湖北工程学院 The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A green and recyclable chitosan supported catalyst for the borylation of α,β-unsaturated acceptors in water;Pengyu Xu et al;《atalysis Communications》;20160803;第86卷;第23-26页 *
Copper-Catalyzed Asymmetric Hydroboration of α-Dehydroamino Acid Derivatives: Facile Synthesis of Chiral β- Hydroxy- α-amino Acids;Zhi-Tao He et al;《Org. Lett.》;20141231;第16卷;第1426-1429页 *
Impregnated Copper on Magnetite as Recyclable Catalyst for the Addition of Alkoxy Diboron Reagents to C -C Double Bonds;Rafael Cano et al;《J. Org. Chem.》;20101231;第75卷;第3458-3460页 *
纯水中二价铜催化α,β-不饱和化合物硼加成反应的研究进展;严沣等;《化学与生物工程》;20180808(第8期);第1-7页 *

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