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Green method for catalyzing dithioacetal/ketone to be deprotected into carbonyl compound

A technology for catalyzing dithioacetal and carbonyl compounds, which is applied in the field of green synthesis of catalyzing the deprotection of dithioacetal/ketone into carbonyl compounds, and can solve the problem of limiting the application of thioacetal/ketone protecting groups and poor functional group compatibility , reagents are expensive and other problems, to achieve good application prospects, good tolerance, easy to obtain the effect of reagents

Pending Publication Date: 2022-03-04
BEIJING UNIV OF CHINESE MEDICINE
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0003] At present, although many methods have been developed for the deprotection of thioacetal / ketone compounds, such as using heavy metal salts such as Hg(II), Zn(II), Ag(I), Ga(III), or using SeO 2 , (PhSeO) 2 O and other toxic reagents, or use NBS, hypervalent iodine reagents, etc., but these methods have some disadvantages, such as expensive reagents, long reaction time, poor functional group compatibility, unfriendly to the environment, etc., these shortcomings severely limit the use of thioacetals / Application of ketone protecting group in the field of organic synthesis

Method used

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  • Green method for catalyzing dithioacetal/ketone to be deprotected into carbonyl compound
  • Green method for catalyzing dithioacetal/ketone to be deprotected into carbonyl compound
  • Green method for catalyzing dithioacetal/ketone to be deprotected into carbonyl compound

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Experimental program
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Effect test

Embodiment 1

[0028]

[0029] Add 40mL of ethanol and 1a (4mmol, 0.92g) into a 100mL round bottom flask in sequence, stir well, then add CeBr to the mixture of the two in sequence 3 (0.4mmol, 0.152g), H 2 o 2 Aqueous solution (30wt%, 8mmol, 0.82mL), stirred at room temperature for 10min. After the reaction is complete, use Na 2 S 2 o 3 solution (0.1M, 20 mL) to quench the reaction and extract with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 x 50 mL). After combining the organic phases, they were successively washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 1b (yield: 99%). The characterization data of this compound are as follows: 1 H-NMR (400MHz, Chloroform-d) δ7.93-7.80(m, 2H), 7.48-7.32(m, 2H), 2.56(s, 3H). 13 C-NMR (100MHz, Chloroform-d) δ196.8, 139.6, 135.5, 129.8, 128.9, 26.6. cm -1 ; HRMS (ESI + )(m / z)calcd.for C 8 ...

Embodiment 2

[0031]

[0032] Add 40mL of ethanol and 2a (4mmol, 1.1g) into a 100mL round bottom flask in turn, stir well, and then add CeBr to the mixture of the two in turn 3 (0.4mmol, 0.152g), H 2 o 2 Aqueous solution (30wt%, 8mmol, 0.82mL), stirred at room temperature for 10min. After the reaction is complete, use Na 2 S 2 o 3 solution (0.1M, 20 mL) to quench the reaction and extract with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 x 50 mL). After combining the organic phases, they were successively washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 2b (yield: 90%). The characterization data of this compound are as follows: 1H-NMR (400MHz, Chloroform-d) δ7.89-7.71(m, 2H), 7.64-7.53(m, 2H), 2.57(s, 3H). 13 C-NMR (100MHz, Chloroform-d) δ197.1, 135.9, 132.0, 129.9, 128.4, 26.6. -1 ; HRMS (ESI + )(m / z)calcd.for C 8 h 8 BrO[M...

Embodiment 3

[0034]

[0035] Add 30mL of ethanol and 3a (3mmol, 0.97g) into a 100mL round bottom flask in turn, stir well, and then add CeBr to the mixture of the two in turn 3 (0.3mmol, 0.114g), H 2 o 2 Aqueous solution (30wt%, 6mmol, 0.61mL), stirred at room temperature for 10min. After the reaction is complete, use Na 2 S 2 o 3 solution (0.1 M, 15 mL) to quench the reaction and extract with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 x 50 mL). After combining the organic phases, they were successively washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 3b (yield: 92%). The characterization data of this compound are as follows: 1 H-NMR (400MHz, Chloroform-d) δ7.88-7.76(m, 2H), 7.71-7.60(m, 2H), 2.56(s, 3H). 13 C-NMR (100MHz, Chloroform-d) δ197.4, 138.0, 136.5, 129.8, 101.2, 26.6. -1 ; HRMS (ESI + )(m / z)calcd.for C 8 h 8 IO...

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Abstract

The invention provides a green method for catalyzing dithioacetal / ketone to be deprotected into a carbonyl compound, and belongs to the field of green organic synthesis. According to the method, a green solvent ethanol is taken as a reaction solvent, hypobromous acid generated in situ by a synergistic catalysis system H2O2-CeBr3 is taken as a direct oxidant under neutral, open and room-temperature conditions, and the dithioacetal / ketone compound is quickly oxidized into a corresponding carbonyl compound. The solvent ethanol used in the method is green and environment-friendly, the reagents H2O2 and CeBr3 are cheap and easy to obtain, the reaction cost is low, the method is mild and efficient, the substrate application range is wide, the product yield is high, operation is easy and convenient, application of dithioacetal / ketone protecting groups in modern organic synthesis is further expanded, and the method has wide application prospects.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a green synthesis method for catalyzing the deprotection of dithioacetal / ketone into carbonyl compounds. Background technique [0002] In the field of organic synthesis, especially in multi-step organic synthesis reactions, the protection and deprotection of various functional groups is a common practice. Among various protecting groups, thioacetal / ketone compounds play a crucial role in the total synthesis of natural products, and their deprotection of carbonyl groups, especially under mild reaction conditions, has always been an organic Research hotspots in the field of synthesis. [0003] At present, although many methods have been developed for the deprotection of thioacetal / ketone compounds, such as using heavy metal salts such as Hg(II), Zn(II), Ag(I), Ga(III), or using SeO 2 , (PhSeO) 2 O and other toxic reagents, or use NBS, hypervalent iodine rea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/56C07C45/51C07C49/807C07C49/67C07C47/546C07C47/575C07C67/313C07C69/76
CPCC07C45/567C07C45/518C07C67/313C07C2602/08C07C2603/50C07C49/807C07C69/76C07C47/546C07C47/575C07C49/67Y02P20/55
Inventor 赵国栋雷海民王亚欣
Owner BEIJING UNIV OF CHINESE MEDICINE
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