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3-substituted 3-vinyl-2-hydroxy-1-aryl acetone and synthetic method thereof

A technology of aryl acetone and synthesis method, which is applied in the field of synthesis of chiral compounds, can solve the problems of poor reaction selectivity, unfavorable drug synthesis and screening, increased economic cost and time cost, etc., and achieves mild reaction conditions, shortened process, and easy synthesis low cost effect

Active Publication Date: 2017-01-11
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The above method can only obtain α-allylated derivatives of hydroxyl ketones with continuous chiral centers through multi-step reactions or reactions with substrates with protective groups, which not only increases the economic cost and time cost of production, but also has reaction The problem of poor selectivity is not conducive to the synthesis and screening of drugs

Method used

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  • 3-substituted 3-vinyl-2-hydroxy-1-aryl acetone and synthetic method thereof
  • 3-substituted 3-vinyl-2-hydroxy-1-aryl acetone and synthetic method thereof
  • 3-substituted 3-vinyl-2-hydroxy-1-aryl acetone and synthetic method thereof

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Experimental program
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Effect test

Embodiment 1

[0030] 1.8 mg of L1 ligand was added to a 5 ml reaction flask, and 0.3 ml of toluene and 12.5 μl of diethyl zinc solution (0.0125 mmol) were added thereto under nitrogen protection, and stirred at 25° C. for 30 minutes to obtain a zinc catalyst.

[0031] Add 3.4mg (1,5-cyclooctadiene) iridium chloride dimer and 5.4mg (R,R,R)-L6 ligand to a 10ml reaction bottle, and add 0.5ml Tetrahydrofuran and 0.5ml of n-propylamine were stirred at 50°C for 30 minutes, and the solvent was concentrated and spin-dried to obtain an iridium catalyst.

[0032] Under nitrogen protection conditions, 48.0mg cinnamyl methyl carbonate, 40.8mg 2-hydroxy-1-acetophenone, 100mg Molecular sieves, zinc catalyst, iridium catalyst and 2ml tetrahydrofuran were added into a 10ml reaction flask, and stirred at 25°C for 12 hours. The reaction solution was concentrated and spin-dried to dry the solvent, and passed through a silica gel column to obtain a purified product with a yield of 41%, a dr value of 1:1, and...

Embodiment 2

[0035]2.5 mg of L2 ligand was added to a 5 ml reaction bottle, and 0.3 ml of toluene and 12.5 μl of diethyl zinc solution (0.0125 mmol) were added thereto under nitrogen protection, and stirred at 25° C. for 30 minutes to obtain a zinc catalyst.

[0036] Add 3.4mg (1,5-cyclooctadiene) iridium chloride dimer and 5.4mg (R,R,R)-L6 ligand to a 10ml reaction bottle, and add 0.5ml Tetrahydrofuran and 0.5ml of n-propylamine were stirred at 50°C for 30 minutes, and the solvent was concentrated and spin-dried to obtain an iridium catalyst.

[0037] Under nitrogen protection conditions, 48.0mg cinnamyl methyl carbonate, 40.8mg 2-hydroxy-1-acetophenone, 100mg Molecular sieves, zinc catalyst, iridium catalyst and 2ml tetrahydrofuran were added into a 10ml reaction flask, and stirred at 25°C for 12 hours. The reaction solution was concentrated and spin-dried to dry the solvent, and passed through a silica gel column to obtain a purified product with a yield of 49%, a dr value of 1:1, and...

Embodiment 3

[0039] 3.3 mg of L3 ligand was added to a 5 ml reaction bottle, and 0.3 ml of toluene and 12.5 μl of diethyl zinc solution (0.0125 mmol) were added thereto under nitrogen protection, and stirred at 25° C. for 30 minutes to obtain a zinc catalyst.

[0040] Add 3.4mg (1,5-cyclooctadiene) iridium chloride dimer and 5.4mg (R,R,R)-L6 ligand to a 10ml reaction bottle, and add 0.5ml Tetrahydrofuran and 0.5ml of n-propylamine were stirred at 50°C for 30 minutes, and the solvent was concentrated and spin-dried to obtain an iridium catalyst.

[0041] Under nitrogen protection conditions, 48.0mg cinnamyl methyl carbonate, 40.8mg 2-hydroxy-1-acetophenone, 100mg Molecular sieves, zinc catalyst, iridium catalyst and 2ml tetrahydrofuran were added into a 10ml reaction flask, and stirred at 25°C for 12 hours. The reaction solution was concentrated and spin-dried to dry the solvent, and the purified product was obtained by passing through a silica gel column with a yield of 44%, a dr value o...

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Abstract

The invention provides a method for synthesizing 3-substituted 3-vinyl-2-hydroxy-1-aryl acetone, and the reaction route is shown as follows: (please see the formula in the description), wherein Ar is phenyl, thienyl or substituted phenyl; R is methyl, phenyl, furyl or substituted phenyl. Compared with the existing allyl synthesis of alpha position of hydroxyketone, the synthetic method has the advantages of having hydroxyl group, requiring no protection, and being good in the substrate applicability, mild in the reaction conditions, simple in operation and low in the synthetic cost, and stereo divergent synthesis of 3-substituted 3-vinyl-2-hydroxy-1-aryl acetone with continuous chiral centers can be achieved only through one-step reaction, namely, any one of the four spatial configurations of the product is synthesized according to the need. The product can be directly applied to the selectivity synthesis of the broad-spectrum inhibitor hinokiresinol medicine, and reduce the original process.

Description

technical field [0001] The invention relates to a 3-substituted 3-vinyl-2-hydroxyl-1-aryl acetone and a synthesis method thereof, belonging to the technical field of synthesis of chiral compounds. Background technique [0002] Hydroxyketone derivatives are an important class of ketone compounds. Hydroxyketone derivatives containing continuous chiral centers exist in large quantities in natural products and medicines, such as: broad-spectrum inhibitor isocypressin (Nyasol) parasiticide Milbemycins for insects, Sesquiterpene(+)-Albicanol for fish, Antibiotic Echinosporin, Breynolide, lignans for antitumor drugs Alcohol (Wikstromol), α-hydroxylactone Chaparrin, intermediate of glycopeptide synthesis (Bulgecinine), antitumor antibiotics (Macbecin I and II) and anti-inflammatory drug leukotriene B4 (Leukotriene B4). (Franklin A. Davis, Bang-Chi Chen, Chem. Rev., 1992, 92, 919-934.) Therefore, it is of great significance to develop methods for synthesizing these compounds. [00...

Claims

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Application Information

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IPC IPC(8): C07C45/68C07C49/82C07C49/84C07C201/12C07C205/45C07D307/46B01J31/30B01J31/22
CPCB01J31/2217B01J31/30B01J2231/52B01J2531/26B01J2531/70C07C45/68C07C201/12C07D307/46C07C49/82C07C49/84C07C205/45
Inventor 张万斌何睿张晓霍小红
Owner SHANGHAI JIAO TONG UNIV
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