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Synthesis method of chiral spiro tetrahydrofuran-pyrazolone compound

A furan pyrazolone and a synthesis method technology are applied in the field of catalytic synthesis of a chiral spirocyclic tetrahydrofuran pyrazolone compound to achieve the effects of improving reaction yield, excellent enantioselectivity and chemical selectivity

Pending Publication Date: 2022-06-07
SUZHOU UNIV
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Problems solved by technology

In the field of organic synthesis research, catalysts complexed with metals and chiral ligands can be applied to the synthesis of many organic compounds; however, there is no literature on the efficient synthesis of chiral spirocyclic tetrahydrofuran pyrazolone compounds catalyzed by metal palladium complexes. to report

Method used

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  • Synthesis method of chiral spiro tetrahydrofuran-pyrazolone compound
  • Synthesis method of chiral spiro tetrahydrofuran-pyrazolone compound
  • Synthesis method of chiral spiro tetrahydrofuran-pyrazolone compound

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Experimental program
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Effect test

Embodiment 1

[0040]

[0041] The reaction flask was sequentially added tetrakistriphenylphosphine palladium (5.7 mg, 0.005 mmol), chiral bisphosphoramidite (7.6 mg, 0.01 mmol), 2 mL of m-xylene was added, stirred at room temperature for 1 hour, and then added 1a (28.5 mg, 0.15 mmol), 2a (26.2 mg, 0.1 mmol), reacted at 10 °C for 24 hours. The target product 3a (yield: 35.9 mg, 88%) can be obtained by simple column chromatography (eluent: ethyl acetate: petroleum ether=100:1) in the reaction system as a brown solid with 99% enantioselectivity , the diastereoselectivity is >20:1.

[0042] The product 3a was analyzed and the results were as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J = 8.4Hz, 1H), 7.45 (t, J = 7.6 Hz, 3H), 7.28 (m, 8H), 6.92 (d, J = 8.0 Hz, 1H), 6.78 (dd, J = 17.2, 10.8 Hz, 1H), 5.82 (s, 1H), 5.37 (d, J = 10.4 Hz, 1H), 5.01 (d, J = 8.8 Hz, 1H), 4.92 (d, J = 4.4 Hz, 1H), 4.89 (d, J = 4.0 Hz, 1H),1.63 (s, 3H) ; 13 C NMR (101 MHz, CDCl 3 ) δ 170.6, ...

Embodiment 2

[0050]

[0051] The reaction flask was sequentially added tetrakistriphenylphosphine palladium (5.7 mg, 0.005 mmol), chiral bisphosphoramidite (7.6 mg, 0.01 mmol), 2 mL of m-xylene was added, stirred at room temperature for 1 hour, and then added 1b (30.6 mg, 0.15 mmol), 2a (26.2 mg, 0.1 mmol), reacted at 10 °C for 24 hours. The target product 3b was obtained by simple column chromatography (eluent: ethyl acetate: petroleum ether=100:1) in the reaction system (the yields were 33.7 mg, 80%, respectively) as a white solid with an enantioselectivity of 94 %, diastereoselectivity >20:1.

[0052] The product 3b was analyzed and the results were as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.88 (d, J = 8.0Hz, 1H), 7.46 (t, J = 8.0 Hz, 2H), 7.34–7.23 (m, 6H), 7.10 (d, J = 7.6 Hz, 2H), 6.81 (d, J = 7.6 Hz, 2H), 6.76 (dd, J = 17.2, 10.8 Hz, 1H ), 5.82 (s, 1H), 5.36 (d, J = 10.6 Hz, 1H), 5.00 (d, J = 8.8 Hz, 1H), 4.91 (m, 2H), 2.31(s, 3H), 1.65 (s, 3H) ; 13 C NMR (101...

Embodiment 3

[0054]

[0055] The reaction flask was sequentially added tetrakistriphenylphosphine palladium (5.7 mg, 0.005 mmol), chiral bisphosphoramidite (7.6 mg, 0.01 mmol), 2 mL of m-xylene was added, stirred at room temperature for 1 hour, and then added 1d (40.2 mg, 0.15 mmol), 2a (26.2 mg, 0.1 mmol), reacted at 10 °C for 24 hours. The target product 3d (yield 40.8 mg, 84%, respectively) can be obtained by simple column chromatography (eluent: ethyl acetate: petroleum ether=100:1) in the reaction system as a white solid with an enantioselectivity of 95 %, diastereoselectivity >20:1.

[0056] The product 3d was analyzed and the results were as follows: 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.0Hz, 2H), 7.44 – 7.37 (m, 4H), 7.23 (m, 6H), 6.76 (d, J = 8.8 Hz, 2H), 6.72(dd, J = 17.6, 10.8 Hz, 1H), 5.78 (s, 1H), 5.34 (d, J = 10.4 Hz, 1H), 4.92(d, J = 8.8 Hz, 1H), 4.88–4.79 (m, 2H), 1.60 (s, 3H); 13C NMR (101 MHz, CDCl3) δ IR (KB)ν; max : 3015, 2923, 1703, 1595, 1498, 13...

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Abstract

The invention discloses a synthesis method of a chiral spiro tetrahydrofuran pyrazolone compound, which specifically comprises the following steps: by taking vinyl cyclic carbonate and alpha, beta-unsaturated pyrazolone as reactants, Pd (PPh3) 4 as a metal and a chiral phosphorus ligand as a chiral ligand, reacting in an organic solvent to obtain the chiral spiro tetrahydrofuran pyrazolone compound. The method disclosed by the invention has the advantages of simple and easily available raw materials, mild reaction conditions, simple and convenient post-treatment, wide applicable substrate range, high yield and high enantioselectivity; the synthesized product can be used for synthesizing an intermediate of a medicine.

Description

technical field [0001] The invention relates to the synthesis of spirocyclic pyrazolone compounds, in particular to a catalytic synthesis method of a chiral spirocyclic tetrahydrofuran pyrazolone compound. Background technique [0002] Pyrazolinone compounds have attracted the attention of chemists based on their own dinitrogen atomic lactam structure, and have great application value in the field of biomedicine. The spiropyrazolone compounds also have great application value. Existing common sense shows that active molecules containing spiropyrazolone skeleton have antibacterial, anti-inflammatory, analgesic, antagonistic, antitumor and other effects. Therefore, the development of high-efficiency synthetic methods for the synthesis of spiropyrazolone structures has aroused great interest in researchers. [0003] In the prior art, Rios research group reported the 4-position unsubstituted pyrazolone and α,β - Tandem Michael addition of unsaturated aldehydes - aldol condens...

Claims

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Application Information

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IPC IPC(8): C07D491/107
CPCC07D491/107C07B2200/07
Inventor 王兴旺吕昊朋
Owner SUZHOU UNIV
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