Method for biologically catalyzing hydrocarbylation of catechols

A technology of biocatalysis and biocatalyst, applied in the field of biocatalytic transformation

Active Publication Date: 2016-11-23
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Utilizing this method to prepare hydrocarbylated products requires the consumption of stoichiometric SAM analogs. If the recycling...

Method used

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  • Method for biologically catalyzing hydrocarbylation of catechols
  • Method for biologically catalyzing hydrocarbylation of catechols
  • Method for biologically catalyzing hydrocarbylation of catechols

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] The purified COMT (final concentration 6.3mg / mL), Allyl-SAM (final concentration 4.0mM), catechol (final concentration 4.0mM) in 30mL containing 50mM Tris-Cl, pH 8.0, 1mM MgCl 2 , in a solution of 0.5mM EDTA, reacted at 40°C for 1h. Add 30mL of NaCl with a mass concentration of 26% to terminate the reaction, centrifuge to remove the precipitate, extract the supernatant ethyl acetate three times, remove the solvent by rotary evaporation of the organic phase, and separate the crude product through silica gel column chromatography, ethyl acetate / petroleum ether (1 / 10, v / v) was used as the eluent to obtain the target product 2-(allyloxy)phenol 1 with a yield of 48.3%.

[0049]

[0050] target product 1 1 H NMR (400MHz, CDCl 3 )δ4.61(d, J=5.2Hz, 2H), 5.42(dd, J=13.6, 36.6Hz, 2H), 5.64(s, 1H), 6.01-6.11(m, 2H), 6.79-6.94(m ,4H); 13 C NMR (160MHz, CDCl 3 )δ69.8, 112.2, 114.7, 118.2, 120.0, 121.7, 132.8, 145.5, 146.0; HRMS: Calculated for C 9 h 11 o 2 ([M+H] + ): 15...

Embodiment 2

[0052]The purified COMT (final concentration 8.5mg / mL), Allyl-SAM (final concentration 4.0mM), 2,3-dihydroxynaphthol (final concentration 6.0mM), allyl bromide (final concentration 4mM), Al 2 o 3 (0.4mM) Contains 60% 50mM NaH in 20mL 2 PO 4 , pH 5.5, 1 mM MgCl 2 , 1mM DTT, 40% methanol solution, stirred at 10°C for 72h. Add 20mL of 26% NaCl to terminate the reaction, centrifuge to remove the precipitate, extract the supernatant ethyl acetate three times, remove the solvent by rotary evaporation of the organic phase, separate the crude product through silica gel column chromatography, ethyl acetate / petroleum ether (1 / 10, v / v) was used as eluent to obtain the target product 2-(allyloxy)naphthol 2 with a yield of 80.2%.

[0053]

[0054] target product 2 1 H NMR (400MHz, CDCl 3 )δ4.75(dt,J 1 =5.6Hz,J 2 =1.2Hz,2H),5.35-5.50(m,2H),5.93(s,1H),6.09-6.18(m,1H),7.13(s,1H),7.27(s,1H),7.28-7.34( m,2H),7.66(dd,J=7.4,1.8Hz,2H); 13 CNMR (100MHz, CDCl 3 )δ69.7, 107.0, 109.5, 1...

Embodiment 3

[0056] The whole cell lysate (final concentration 5.8mg / mL) of Escherichia coli recombinant strain expressing COMT, Allyl-SAM (final concentration 4.0mM), dopamine (final concentration 4.0mM) in 30mL containing 50mM Tris-Cl, pH 8.5, 1mM DTT, 20mM MgCl 2 , in a solution of 10mM EDTA, after reacting at 37°C for 5h, add 30mL of 26% NaCl to terminate the reaction, centrifuge to remove the precipitate, extract the supernatant with ethyl acetate three times, remove the solvent by rotary evaporation of the organic phase, and separate the crude product by silica gel column chromatography. Methanol / dichloromethane (1 / 10, v / v) was used as the eluent to obtain the target product 3m with a yield of 20.1%.

[0057]

[0058] Target product 3m 1 H NMR (400MHz,D 2 O) δ3.15(t, J=7.4Hz, 2H), 4.55(t, J=6.0Hz, 2H), 5.21-5.34(m, 2H), 5.93-6.04(m, 1H), 6.72-6.93( m,3H); HRMS: Calculated for C 11 h 16 NO 2 ([M+H] + ):194.1181;obtained:194.1176;

[0059] HPLC measures the ratio of the two...

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Abstract

The invention discloses a method for biologically catalyzing hydrocarbylation of catechols. The method comprises the steps that catechol-O-methyltransferase serves as a catalyst, an S-adenosyl methionine analogue serves as a hydrocarbyl donor, hydrocarbylation of the catechols is achieved through enzymatic catalysis, and corresponding products are obtained. The method has the advantages of being mild in reaction condition, environmentally friendly, easy to operate, wide in applicable range of raw materials, high in catalytic conversion rate and good in chemical and regional selectivity; in addition, cyclic regeneration of the hydrocarbyl donor can be achieved by adding a solid acid catalyst.

Description

technical field [0001] The invention relates to the technical field of biocatalytic conversion, in particular to a method for biocatalyzing the alkylation of catechol compounds. Background technique [0002] Catechol derivatives widely exist in nature and have the functions of anti-oxidation, anti-aging, and elimination of harmful free radicals. Compounds based on their parent phenolic hydroxyl modification are also mostly used to prepare new pharmaceutical intermediates and natural products with biological activity. Li et al. synthesized a series of alkylated catechols for the activity evaluation of influenza virus neuraminidase inhibitors (J.Li, et al.Mar.Drugs 2011,9,1887-1901); et al synthesized glycosylated dopamine for potential anti-Parkinson drug research (C. et al.Carbohydr.Res.2000,327,353-365); Fumeaux et al. synthesized 24 potential human coffee polyphenol metabolites based on various modifications of 3,4-dihydroxybenzaldehyde phenolic hydroxyl groups (R.Fume...

Claims

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Application Information

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IPC IPC(8): C12P7/22C12P13/00C12P7/42C12P11/00C12P17/04C12P13/02C12P7/26
Inventor 赵宗保张祎昕刘武军默罕默德·索黑尔
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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