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Method for selectively preparing alpha-acyloxylation or beta-acyloxylation product of enamine ketone compound

A technology of acyloxylation and enaminone, which is applied in the field of organic synthesis methodology, can solve problems such as failure to pass, and achieve the effects of mild reaction conditions, high yield, and simple process conditions

Active Publication Date: 2018-04-17
NANJING UNIV OF TECH
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Problems solved by technology

However, in 1978, the Beat Hurni team at the Institute of Organic Chemistry at the University of Bern in Germany reported the use of acetylenyl ketones and carboxylic acids for a molecule of Michael addition to generate α-acyloxylated (β-acyloxylated) enamines , and then further rearranged and migrated to obtain β-acetoxy α, β-unsaturated amide compounds, although this method is the first to report the rearrangement of α-acyloxylated (β-acyloxylated) enaminones Reaction, but the first step is obtained by Michael addition, not through sp 2 C-H activation gives this compound

Method used

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  • Method for selectively preparing alpha-acyloxylation or beta-acyloxylation product of enamine ketone compound
  • Method for selectively preparing alpha-acyloxylation or beta-acyloxylation product of enamine ketone compound
  • Method for selectively preparing alpha-acyloxylation or beta-acyloxylation product of enamine ketone compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] The first part: selective preparation of α-acyloxylation products of enaminone compounds;

[0034] Add (E)-1-phenyl-3-dimethylamino-2-propenone and PIDA in the ratio of equivalent ratio 1.0:1.3 (weigh 0.20mmol and 0.26mmol respectively) into the round bottom flask, then add the reaction The solvent trifluoroethanol (TFE) (2.0mL) is stirred in air at room temperature for 0.5 to 3 hours to selectively obtain compound (Z)-1-phenyl-2-acetoxy-3-dimethylamine Base-2-propenone, the yield is 83%; 1 H NMR spectrum see figure 1 , 13 C NMR spectrum see figure 2 .

[0035] The second part: selective preparation of β-acyloxylation products of enaminone compounds;

[0036] (E)-1-phenyl-3-dimethylamino-2-propenone and PIDA were added to the round bottom flask according to the ratio of equivalent ratio 1.0:2.0 (weighed 0.20mmol and 0.40mmol respectively), and then added 2.0 Equivalent water (0.40mmol) and reaction solvent acetonitrile (2.0mL), stirred in air at room temperature ...

Embodiment 2

[0038] The first part: selective preparation of α-acyloxylation products of enaminone compounds;

[0039](E)-1-phenyl-3-(1-tetrahydropyrrolyl)-2-propenone and PIDA were added to the round bottom flask according to the ratio of equivalent ratio 1.0:1.3 (weighed 0.20mmol and 0.26mmol respectively) , then add the reaction solvent trifluoroethanol (TFE) (2.0mL) and stir in the air at room temperature for 0.5 to 3 hours, the compound (Z)-1-phenyl can be selectively obtained in a higher yield of 71%. -2-Acetoxy-3-(1-tetrahydropyrrolyl)-2-propenone, the yield is 71%;

[0040] The second part: selective preparation of β-acyloxylation products of enaminone compounds;

[0041] Add (E)-1-phenyl-3-(1-tetrahydropyrrolyl)-2-propenone and PIDA in the ratio of 1.0:2.0 (weigh 0.20mmol and 0.40mmol respectively) into the round bottom flask , then add 2.0 equivalents of water (0.40mmol) and reaction solvent acetonitrile (2.0mL), and stir in air at room temperature for 3 to 6 hours to selective...

Embodiment 3

[0043] The first part: selective preparation of α-acyloxylation products of enaminone compounds;

[0044] Add (E)-1-(4-nitrophenyl)-3-dimethylamino-2-propenone and PIDA to the round bottom at the ratio of equivalent ratio 1.0:1.3 (weigh 0.20mmol and 0.26mmol respectively) In the flask, add the reaction solvent trifluoroethanol (TFE) (2.0mL) and stir in the air at room temperature for 0.5 to 3 hours to selectively obtain the compound (Z)-1-(4-nitrophenyl) -2-acetoxy-3-dimethylamino-2-propenone, the yield is 86%;

[0045] The second part: selective preparation of β-acyloxylation products of enaminone compounds;

[0046] Add (E)-1-(4-nitrophenyl)-3-dimethylamino-2-propenone and PIDA to the round bottom at an equivalent ratio of 1.0:2.0 (weigh 0.20mmol and 0.40mmol respectively) In the flask, add 2.0 equivalents of water (0.40mmol) and reaction solvent acetonitrile (2.0mL), and stir in air at room temperature for 3 to 6 hours to selectively obtain compound (Z)-N,N-di Methyl-3-(...

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Abstract

The invention relates to a method for selectively preparing an alpha-acyloxylation or beta-acyloxylation product of an enamine ketone compound. When the alpha-acyloxylation product of the enamine ketone compound is selectively prepared, the enamine ketone compound and PIDA are added into trifluoroethanol according to the proportion of 1.0:1.3 and stirred for 0.5-3 hours at room temperature to obtain the alpha-acyloxylation product. When the beta-acyloxylation product of the enamine ketone compound is selectively prepared, the enamine ketone compound and PIDA are added into a reaction vessel according to the proportion of (1:1)-(1:2), water and solvents are added, and the materials are stirred for 3-6 hours at the room temperature to obtain the beta-acyloxylation product. The process is simple, reaction conditions are mild, the alpha-acyloxylation product of the enamine ketone compound can be effectively prepared in a high-yield manner, and the beta-acyloxylation product of the enamineketone compound can be selectively rearranged to obtain a beta-acyloxylation alpha, beta-unsaturated amide compound.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis methodology, in particular to a 2 Process for the preparation of alpha-acyloxylation or beta-acyloxylation products of enaminone compounds by C-H functionalization. Background technique [0002] Because the enaminone compound retains the active enamino segment, a variety of functional group transformations can occur, and the existence of the conjugated carbonyl makes it relatively stable. In recent years, research on enaminone compounds as starting materials for synthetic methodology has begun to emerge. In this field of research, Wan Jieping's team from Jiangxi Normal University has made a lot of research progress by using this substrate. [0003] In 2014, Wan Jieping’s research group used enaminone compounds as substrates to obtain the green synthesis of 1,3,5-triacylbenzene compounds in an aqueous solution of 2.0 equivalents of lactic acid at 90°C. This method is the largest The adv...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C221/00C07C225/14C07C231/14C07C235/34C07D295/104C07D295/185
CPCC07C221/00C07C231/14C07D295/104C07D295/185C07C225/14C07C235/34
Inventor 姜耀甲王飞孙网彬王一昕罗德平
Owner NANJING UNIV OF TECH
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