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Method for synthesizing 3-hydroxy-3-allyl oxoindole and 3-hydroxy-3-allene oxoindole

An indole oxide, allyl technology, applied in chemical instruments and methods, organic chemistry methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as difficulties and limited expansion of substrates

Pending Publication Date: 2022-05-06
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, few such asymmetric reactions have been catalyzed by Lewis acids
Moreover, it is very difficult to realize the allenylation of isatin by the reaction of isatin with allenylboronic acid pinacol ester using chiral Bronsted acid and organic small molecule catalysts.
In the prior art, only the Hoveyda research group has successfully developed the asymmetric allylation and allenylation of isatin and organoboron reagents using organic small molecule catalysts, but the scope of expansion of substrates is very limited

Method used

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  • Method for synthesizing 3-hydroxy-3-allyl oxoindole and 3-hydroxy-3-allene oxoindole
  • Method for synthesizing 3-hydroxy-3-allyl oxoindole and 3-hydroxy-3-allene oxoindole
  • Method for synthesizing 3-hydroxy-3-allyl oxoindole and 3-hydroxy-3-allene oxoindole

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preparation example Construction

[0094] In the present invention, the preparation method of the chiral zinc complex preferably comprises the following steps:

[0095] a) After reacting the zinc salt, the basic compound and the ligand in a solvent, a chiral zinc complex is obtained.

[0096] In the present invention, the zinc salt preferably includes one or more of zinc bromide, zinc fluoride, zinc chloride, zinc trifluoromethanesulfonate, zinc nitrate, zinc sulfate and zinc acetate, more preferably bromine Zinc chloride, zinc fluoride, zinc chloride, zinc trifluoromethanesulfonate, zinc nitrate, zinc sulfate, or zinc acetate.

[0097] In the present invention, the basic compound preferably includes cesium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, potassium tert-butoxide, triethylenediamine, triethylamine, piperidine, 1,8-diazabicyclo [5.4.0] One or more of undec-7-ene, N,N-diisopropylethylamine and N-ethylmorpholine, more preferably cesium carbonate, lithium carbonate, sodium carbo...

Embodiment 1

[0191] In a 10mL reaction tube, add zinc triflate (3.6mg, 0.01mmol), ligand (L 2 , 4.6mg, 0.01mmol), acetone (1.0mL), cesium carbonate (3.3mg, 0.01mmol) were stirred at room temperature for 2h. Then, isatin 1a (16.1mg, 0.1mmol), allylboronic acid pinacol ester 2a (42.0mg, 0.25mmol) and 10 microliters of methanol were added successively at 10°C. After the reaction was completed (TLC tracking detection), Extracted with ethyl acetate, extracted with saturated brine, dried over anhydrous sodium sulfate, and spin-dried the obtained residue to pass through the column with petroleum ether / ethyl acetate system as eluent to obtain a white solid (S)-3a (98% yield , 19.9 mg, 93% ee).

[0192] Utilize nuclear magnetic resonance to analyze the target product (S)-3a that obtains in embodiment 1, obtain its proton nuclear magnetic resonance spectrum figure, as figure 1 shown.

[0193] see figure 1 , figure 1 It is the proton nuclear magnetic resonance spectrum of the target product (S)-...

Embodiment 2

[0199] In a 10mL reaction tube, add zinc triflate (3.6mg, 0.01mmol), ligand (L 2 , 4.6mg, 0.01mmol), acetone (1.0mL), cesium carbonate (3.3mg, 0.01mmol) were stirred at room temperature for 2h. Then, isatin 1b (22.3mg, 0.1mmol), allylboronic acid pinacol ester 2a (42.0mg, 0.25mmol) and 10 microliters of methanol were added successively at 10°C. After the reaction was completed (TLC tracking detection), Extracted with ethyl acetate, extracted with saturated brine, dried over anhydrous sodium sulfate, and spin-dried the obtained residue to pass through the column with petroleum ether / ethyl acetate system as eluent to obtain a white solid (S)-3b (97% yield , 25.7 mg, 89% ee).

[0200] Utilize nuclear magnetic resonance to analyze the target product (S)-3b that obtains in embodiment 2, obtain its proton nuclear magnetic resonance spectrum figure, as image 3 shown.

[0201] see image 3 , image 3 The proton nuclear magnetic resonance spectrum of the target product (S)-3b pre...

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Abstract

The invention provides a chiral zinc complex. The chiral zinc complex has a structure as shown in a formula (CI) or a formula (CII). The chiral zinc complex is used as a catalyst, asymmetric allylation and allene reactions of an organic boron reagent and isatin compounds can be efficiently catalyzed, and 3-hydroxy-3-allyl oxoindole and 3-hydroxy-3-allene oxoindole can be obtained with high enantioselectivity. According to the invention, the chiral zinc complex is used as a catalyst for the first time, and 3-hydroxy-3-allyl oxoindole and 3-hydroxy-3-allene oxoindole are prepared through high-enantioselectivity asymmetric allylation and allene of an organic boron reagent on isatin compounds. According to the invention, the lewis acid catalyst system is applied to allylation and allene of isatin for the first time, and excellent enantioselectivity is obtained.

Description

technical field [0001] The invention belongs to the technical field of chiral zinc complex catalysts, and relates to a preparation method of a chiral zinc complex, 3-hydroxy-3-allyl indole oxide and 3-hydroxy-3-alkenyl indole oxide, In particular, it relates to a method for catalytically synthesizing 3-hydroxyl-3-allyloxindole and 3-hydroxyl-3-alkenyloxindole by using a chiral zinc complex with high enantioselectivity. Background technique [0002] Chiral 3-hydroxyindole is an important natural product and precursor of drug molecules, and similar structures can be obtained by 3-hydroxy-3-allyl-oxindole and 3-hydroxy-3-alkenyl-oxindole The conversion of organoboron reagents has many advantages such as easy access, good stability, low toxicity and easy operation. [0003] Therefore, these reagents are widely used in asymmetric synthetic chemistry. In the past, many chemists synthesized 3-hydroxy-3-allyloxindole through the reaction of isatin and allylboronic acid pinacol est...

Claims

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Application Information

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IPC IPC(8): C07F3/06B01J31/22C07B53/00C07D209/38
CPCC07F3/003B01J31/2217C07B53/00C07D209/38B01J2531/26C07B2200/07
Inventor 汪志勇李奎亮
Owner UNIV OF SCI & TECH OF CHINA
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