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Preparation method and application of N-heterocyclic carbene catalyzed cyclopropane skeleton-containing ketene compound

A technology for cyclopropane and compounds, which is applied in the field of preparation and application of cyclopropane skeleton-containing enone compounds catalyzed by azacyclic carbene, and achieves excellent yield, high diastereoselectivity, and good substrate universality

Active Publication Date: 2022-06-21
GUIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

To the best of our knowledge, azacyclic carbene-catalyzed nucleophilic substitution reactions of carbonyl groups to acyclic ketones have not been reported

Method used

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  • Preparation method and application of N-heterocyclic carbene catalyzed cyclopropane skeleton-containing ketene compound
  • Preparation method and application of N-heterocyclic carbene catalyzed cyclopropane skeleton-containing ketene compound
  • Preparation method and application of N-heterocyclic carbene catalyzed cyclopropane skeleton-containing ketene compound

Examples

Experimental program
Comparison scheme
Effect test

preparation Embodiment 1

[0026] Preparation Example 1

[0027] Preparation of N-((Z)-3-((1R,2R)-2-benzoylcyclopropyl)-3-oxo-1-phenylprop-1-en-1-yl)-4-methanol Benzenesulfonamide (I 3 ):

[0028]

[0029] Preparation implementation method and conditions are as follows:

[0030] Weigh 0.20mmol substituted 1-cyclopropyl formaldehyde 1, 0.1mmol substituted sulfonimide 2, 0.02mmol azacyclic carbene catalyst F (9.6mg), 0.12mmol cesium carbonate (39.1mg), 0.02mmol trifluoromethane Zinc sulfonate (7.2mg), 100mg Molecular sieves and 0.20 mmol DQ oxidant (81.7 mg) were added to a 4.0 mL reaction bottle equipped with a magnetic stirrer, 2.0 mL of dichloromethane was added, the reaction wall was shaken gently to mix well, and the reaction was stirred at 35 degrees Celsius for 17 hours. Spin dry after the completion of TLC monitoring reaction, dry loading, separate by column chromatography (eluent polar sherwood oil: ethyl acetate=10:1), obtain target compound I 3 , and calculate the corresponding yield a...

preparation Embodiment 2

[0036] Preparation Example 2

[0037] Substituent R 1 4-OCH 3 -Ph, R 2 For Ph, preparation implementation method and condition are with general embodiment 1;

[0038] N-((Z)-3-((1R,2R)-2-(4-methoxybenzoyl)cyclopropyl)-3-oxo-1-phenylprop-1-ene-1- Base) -4-methylbenzenesulfonamide (I 3b )

[0039]

[0040] 1 H NMR (400MHz, CDCl 3 )δ12.19(s,1H),8.03–7.98(m,2H),7.46–7.40(m,1H),7.36(d,J=8.3Hz,2H),7.33–7.25(m,4H),7.15 (d,J=8.1Hz,2H),7.00–6.95(m,2H),5.72(s,1H),3.89(s,3H),3.27–3.20 (m,1H),2.52(td,J=7.3 ,3.7Hz,1H),2.36(s,3H),1.68–1.61(m,2H).

[0041] 13 C NMR (101MHz, CDCl 3)δ198.6, 195.5, 163.9, 155.3, 144.2, 136.7, 133.4, 130.8, 130.6, 130.0, 129.4, 129.0, 127.9, 127.5, 113.9, 108.5, 55.6, 32.8, 28.4, 21.6, 20.1.

preparation Embodiment 3

[0043] Preparation Example 3

[0044] Substituent R 1 4-CH 3 -Ph,R 2 For Ph, the preparation method and conditions are the same as in General Example 1; N-((Z)-3-((1R,2R)-2-(4-methylbenzoyl)cyclopropyl)-3-oxo -1-phenylprop-1-en-1-yl)benzenesulfonamide (I 3c )

[0045]

[0046] 1 H NMR (400MHz, CDCl 3 )δ12.18(s,1H), 7.95–7.87(m,2H),7.46–7.40(m,1H),7.38–7.33(m,2H),7.33–7.25(m,6H),7.15(d, J=8.2Hz,2H),5.72(s,1H),3.29–3.22(m,1H), 2.57–2.50(m,1H),2.43(s,3H),2.35(s,3H),1.68–1.62 (m,2H).

[0047] 13 C NMR (101MHz, CDCl 3 )δ198.5, 196.8, 155.4, 144.4, 144.2, 136.7, 134.5, 133.4, 130.8, 129.4, 129.4, 129.0, 128.4, 127.9, 127.5, 108.5, 32.9, 28.6, 21.7, 21.6, 20.2.

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Abstract

The invention discloses a preparation method and application of a cyclopropane skeleton-containing ketene compound catalyzed by N-heterocyclic carbene. The structural general formula of the compound is shown in the specification, wherein R1 is phenyl, substituted phenyl or thiophene, and R2 is phenyl, substituted phenyl, 2-naphthyl or 2-thiophene. The compound has the advantages of good universality, excellent yield up to 94%, diastereoselectivity greater than 20: 1, and good biological activity.

Description

technical field [0001] The invention relates to a preparation method and application of a nitrogen-heterocyclic carbene organic small molecule catalyzed synthesis of an enone compound containing a cyclopropane skeleton Background technique [0002] Cyclopropylcarbonyl derivatives widely exist in biologically active natural products and have important applications in drug research and pesticide development (Chem.Rev.2003,103,1625-1648.J.Med.Chem.2016,59, 8712-8756.). For example, S-bioallethrin and cyhalothrin are commercial insecticides, cilastatin sodium is a popular antibiotic drug, and milnacipran hydrochloride, an antidepressant, is also available For the treatment of fibromyalgia symptoms. Efficient synthetic methods of cyclopropylcarbonyl derivatives with diverse functions have received extensive attention. [0003] Nitrogen-heterocyclic carbene (NHC) organocatalysis has been extensively studied in the past two decades, and ketones are among the most important funct...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/36C07C311/16A01N41/08A01P3/00A01P1/00
CPCC07C303/36A01N41/08C07C311/16Y02P20/55
Inventor 金智超吕洁侬应伶池永贵
Owner GUIZHOU UNIV