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Method for synthesizing chiral spirocyclo-oxindole-benzopyran-ketone-3,4-dihydro-pyran compound

A technology for spirocyclic oxindole and pyran compounds, which is applied in the field of synthesis of chiral spirocyclic compounds, can solve the problems of limited application value, low diastereoselectivity, large amount of catalyst and the like, and achieves corresponding selectivity. Excellent, easy-to-use, easy-to-handle effects

Active Publication Date: 2016-12-07
SUZHOU UNIV
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Problems solved by technology

(H.-B. Yang, Y.-Z. Zhao, R.Sang, Y. Wei, M. Shi, Asymmetric Synthesis of Bioxindole-Substituted Hexahydro-furo[2,3- b ] furans via Hydroquinine Anthraquinone-1,4-diyl Di-ether-Catalyzed Domino Annulation of Acylidenoxindoles / Isatins,Acylidenoxindoles and Allenoates. Adv. Synth. Catal., 2014, 356 , 3799-380), but the amount of catalyst used in this reaction is relatively large, and the diastereoselectivity of the reaction is not very high, thus limiting the further application value of this reaction

Method used

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  • Method for synthesizing chiral spirocyclo-oxindole-benzopyran-ketone-3,4-dihydro-pyran compound
  • Method for synthesizing chiral spirocyclo-oxindole-benzopyran-ketone-3,4-dihydro-pyran compound
  • Method for synthesizing chiral spirocyclo-oxindole-benzopyran-ketone-3,4-dihydro-pyran compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026]

[0027] Add quininethiourea (5.9 mg, 0.01 mmol), and 1a (25.9 mg, 0.1 mmol), 2a (16.2 mg, 0.1 mmol) sequentially into the reaction flask, add 1 mL of dichloromethane, and react at room temperature for 12 hours , the reaction system was subjected to simple column chromatography (eluent: petroleum ether: ethyl acetate = 1.8:1) to obtain the target product 3a (36.6 mg), a yellow solid, mp: 198-201 ° C, the yield was 87 %, >20 / 1 dr, 87% ee.

[0028] Add quinine thiourea (5.9 mg, 0.01 mmol) and 1a (25.9 mg, 0.1 mmol) and 2a (16.2 mg, 0.1 mmol) sequentially into the reaction flask, add 1 mL of dichloromethane, and react at zero degrees Celsius for 12 hours, the reaction system was subjected to simple column chromatography (petroleum ether: ethyl acetate = 1.8:1 as the eluent) to obtain the target product 3a (33.3 mg), a yellow solid, mp: 198-201 ℃, and the yield was 79%, >20 / 1 dr, 96% ee.

[0029] Add quinine thiourea (3.0 mg, 0.005 mmol) and 1a (25.9 mg, 0.1 mmol) succ...

Embodiment 2

[0032]

[0033] Add quinine thiourea (3.0 mg, 0.005 mmol) and 1b (28.9 mg, 0.1 mmol) to the reaction flask successively, add 1 mL of dichloromethane, react at minus 20 degrees Celsius for 20 minutes, add 2a (24.3 mg, 0.15 mmol), continue to react for 40 hours, the reaction system can be obtained by simple column chromatography (eluent: petroleum ether: ethyl acetate = 1.6:1) to obtain the target product 3b (42.8 mg), yellow solid, mp: 141- 144 ℃, the yield is 95%, >20 / 1 dr, 98% ee.

[0034] Product 3b is analyzed, and the results are as follows: Measure [Daicel Chiralpak IA, hexane / i -PrOH (70:30), flow rate: 1.0 mL min -1 , λ = 254 nm, t(major) = 12.362, t(minor) = 17.090]; [α] D 25 = + 98.0 (c = 0.50, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ8.48 (s, 0.3H), 8.22 (d, J = 7.2 Hz, 0.4H), 8.18 (d, J = 7.6 Hz, 0.6H), 7.93(d, J = 7.6 Hz, 0.6H), 7.51 – 7.49 (m, 1H), 7.42 (t, J = 7.2 Hz, 0.3H), 7.36(t, J = 7.6 Hz, 0.7H), 7.33 – 7.28 (m, 1H), 7.23 (d, J = 2.9 Hz,...

Embodiment 3

[0036]

[0037] Add quininethiourea (0.002 mmol) and 1c (33.5 mg, 0.1 mmol) to the reaction flask in turn, add 1 mL of dichloromethane, react at minus 20 degrees Celsius for 20 minutes, add 2a (24.3 mg, 0.15 mmol) , continued to react for 38 hours, and the reaction system was subjected to simple column chromatography (eluent: petroleum ether: ethyl acetate = 1.8:1) to obtain the target product 3c (48.3mg), white solid, mp: 141-144 ° C, the yield is 91%, >20 / 1 dr, 96% ee.

[0038] Add quinine thiourea (3.0 mg, 0.005 mmol) and 1c (33.5 mg, 0.1 mmol) in turn to the reaction flask, add 1 mL of dichloromethane, react at minus 20 degrees Celsius for 20 minutes, add 2a (24.3 mg, 0.15 mmol), continued to react for 36 hours, and the reaction system was subjected to simple column chromatography (eluent: petroleum ether: ethyl acetate = 1.8:1) to obtain the target product 3c (48.7 mg), white solid, mp: 141 -144 ℃, 98% yield, >20 / 1 dr, 99% ee.

[0039] Product 3c is analyzed, and the...

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Abstract

The invention discloses a method for synthesizing a chiral spirocyclo-oxindole-benzopyran-ketone-3,4-dihydro-pyran compound. The method comprises the following steps: using an isatin derivative beta, gama-unsaturated alpha-keto ester and 3-hydroxy-4-hydrogen-chromene-4-ketone as reactants, and synthesizing in a solvent under the catalysis of chiral multifunctional chiral quinine thiourea to obtain a product. The method provided by the invention has the advantages of simple and easy obtaining of raw materials, mild reaction conditions, simple and convenient post-treatment, wide range of suitable substrates, high yield and high enantioselectivity, and the synthesized product can be used for synthesizing intermediates of drugs, insecticides and photoelectric materials.

Description

technical field [0001] The invention relates to the synthesis of chiral spiro compounds, in particular to a catalytic synthesis method of chiral spiro oxindole-benzopyran-keto-3,4-dihydro-pyran compounds. Background technique [0002] Chiral oxaspirocyclic oxindole compounds widely exist in natural products and drug molecules, and have anti-tumor, anti-plant virus, plant growth regulation, herbicide, sterilization, enzyme activity inhibition, anti-oxidation and radiation protection, and destruction of biological cell membranes And so on a wide range of biological activities, and has attracted the attention of many scientists. Chiral spiro-oxindole-benzopyran-keto-3,4-dihydro-pyran compounds also have similar potential application value, so an efficient method is chosen to synthesize chiral oxaspiro-oxindole Inole hemiketal compounds have attracted great interest of many chemists, and many synthetic methods have emerged recently. The chiral oxaspirooxindole hemiketal compou...

Claims

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Application Information

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IPC IPC(8): C07D491/20B01J31/02
CPCB01J31/0271B01J2231/324C07D491/20
Inventor 王兴旺殷少杰
Owner SUZHOU UNIV
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