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Chiral aromatic spiroketal compound and preparation method thereof

A technology of compound and spiroketal, which is applied in the field of chiral aromatic spiroketal compound and its preparation, can solve the problems of cumbersome process, uneconomical and environmental protection, etc., and achieve the effect of simple preparation method

Inactive Publication Date: 2012-04-25
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, in order to obtain optically pure chiral aromatic spiroketal compounds, the resolution of racemates is usually required, which is cumbersome and not economical and environmentally friendly.

Method used

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  • Chiral aromatic spiroketal compound and preparation method thereof
  • Chiral aromatic spiroketal compound and preparation method thereof
  • Chiral aromatic spiroketal compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] This embodiment takes the preparation of 3a (its reaction scheme is as follows) as an example to describe in detail the first preparation method of the α, α'-bis(2-hydroxyarylene) ketone compound of the present invention:

[0037]

[0038]Add salicylaldehyde 2a (5.3mL, 51.0mmol), cyclohexanone 1 (2.5mL, 25.0mmol), ethanol (20.0mL), sodium hydroxide aqueous solution (20wt%, 15mL) in the 50mL single-necked bottle, stir at room temperature for 24 hour; add 100mL of distilled water to the reaction system, neutralize to pH=5 with a hydrochloric acid aqueous solution with a concentration of 6mol / L, filter, and dry the solid after washing with distilled water; recrystallize with acetone-petroleum ether to obtain 4.6g of yellow solid 3a, Yield 60%.

[0039] 3a, mp 160-162°C; 1 H NMR (400MHz, acetone-d 6 )δ9.12 (s, 2H), 8.09 (d, J = 16.0Hz, 2H), 7.71 (dd, J = 7.6, 1.2Hz, 2H), 7.34 (d, J = 16.0Hz, 2H), 7.28- 7.24(m, 2H), 6.98(dd, J=8.0, 0.8Hz, 2H), 6.91(t, J=8.0Hz, 2H)ppm; ...

Embodiment 2

[0041] This embodiment takes the preparation of 3b (its reaction scheme is as follows) as an example to describe in detail the second preparation method of α, α'-bis(2-hydroxyarylene) ketone compound of the present invention:

[0042]

[0043] The first step: preparation of compound 4b from compound 2b

[0044] Add 3-methyl salicylaldehyde 2b (5.0g, 0.0367mol), anhydrous triethylamine (6.4mL, 0.044mol), 4-dimethylaminopyridine (90mg, 0.73mmol) and anhydrous di Chloromethane (100mL), cooled to 0°C, slowly added dropwise a dichloromethane solution of tert-butyldimethylsilyl chloride (6.63g, 0.044mol) with stirring; continued stirring for 12 hours after returning to room temperature; adding saturated carbonic acid The reaction was quenched with sodium hydrogen solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated, and then purified by column chromatography to obtain 9.18 g of colorless liquid 4b with a yield of >99%.

[0045]...

Embodiment 3

[0053] The preparation method of reference example 1 respectively prepared substrates 3a, 3d-3g, 3i-3r shown below and the preparation method of reference example 2 respectively prepared substrates 3b, 3c, 3h shown below:

[0054]

[0055] 3c, mp 148-150°C; 1 H NMR (400MHz, DMSO-d 6 )δ9.83(s, 2H), 7.81(s, 2H), 7.22(d, J=7.6Hz, 2H), 6.72(s, 2H), 6.66(d, J=7.6Hz, 2H), 2.78( t, J=5.2Hz, 4H), 2.24(s, 6H), 1.66-1.64(m, 2H)ppm; 13 C NMR (100MHz, DMSO-d 6 )δ 188.9, 156.8, 140.2, 134.4, 131.5, 129.8, 119.8, 119.6, 116.0, 28.2, 23.0, 21.1 ppm.

[0056] 3d, mp 129-130°C; 1 H NMR (400MHz, DMSO-d 6 )δ9.68(s, 2H), 7.80(s, 2H), 7.11(s, 2H), 6.99(dd, J=8.0Hz, 1.6Hz, 2H), 6.80(d, J=8.0Hz, 2H) , 2.80(t, J=5.2Hz, 4H), 2.21(s, 6H), 1.70-1.63(m, 2H)ppm; 13 C NMR (100MHz, DMSO-d 6 ) δ = 189.0, 154.6, 135.1, 131.8, 130.8, 130.2, 127.1, 122.2, 115.4, 28.2, 23.0, 20.2 ppm.

[0057] 3e, mp 130-131°C; 1 H NMR (400MHz, DMSO-d 6 )δ9.71(s, 2H), 7.82(s, 2H), 7.28(d, J=2.8Hz, 2H), 7.22(dd, J=8...

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Abstract

The invention discloses a chiral aromatic spiroketal compound and a preparation method thereof. The compound is a compound of the following formula, or an enantiomer, racemate or diastereomer of the compound. The compound is prepared by carrying out catalytic hydrogenation in an organic solvent under H2 atmosphere by using chiral or achiral metal complex as a catalyst and alpha, alpha'-di(2-hydroxy arylene)ketone as a substrate. The aromatic spiroketal compound disclosed herein can be prepared into a racemic or chiral spiro skeleton ligand as a catalyst for asymmetric catalytic reaction through further derivation. The invention lays the foundation for developing a novel catalyst for asymmetric catalytic reaction, and has industrial application prospects. In addition, the preparation method of the compound is simple, is easy to prepare the chiral aromatic spiroketal compound having high optical purity (ee value is larger than 99 %), and is economic and practical.

Description

technical field [0001] The invention relates to a class of chiral aromatic spirketal compounds and a preparation method thereof, belonging to the technical field of organic chemistry. Background technique [0002] Chiral aromatic spiroketals are important structural units of some natural products, bioactive compounds and chiral ligands. Such as Rubromycins compounds, which contain multiple substituted naphthoquinones and isocoumarin fragments, and are connected by a special chiral aromatic spiroketal skeleton. This unique structure makes this family of compounds have quite good anti-cancer and anti-HIV Biological activities such as reverse transcriptase and anti-DNA helicase (J.Org.Chem.2007, 3801; Nat.Prod.Rep.2010, 27, 1117.). The key to the synthesis of Rubromycins compounds is the construction of the aromatic spiroketal skeleton. The currently reported methods mainly contain the spiroketalization (Tetrahedron Lett.1998, 39, 5429; J.Chem.Soc., Perkin Trans.1 2000, 2681;...

Claims

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Application Information

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IPC IPC(8): C07D493/10C07B53/00
CPCY02P20/55
Inventor 丁奎岭王晓明韩召斌王正
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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