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1,3-cyclodiketone enol ether compound, 1-asymmetirc donor-receptor cyclopropane as well as synthesis methods thereof

A technology for cyclic diketone enol ethers and synthetic methods, which is applied in the field of 1-asymmetric donor acceptor cyclopropane and 1,3-cyclic diketone enol ether compounds, and can solve the problems of limited types and synthetic methods

Active Publication Date: 2019-08-02
ANHUI UNIVERSITY OF TECHNOLOGY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In fact, in domino or multicomponent reactions, 1,3-cyclic diketones are often used as dinucleophiles, where the C2-position is usually the first reactive site; the oxygen atom of 1,3-cyclic diketones The reaction method as the first nucleophilic attack site has been rarely reported so far
However, the types and synthesis methods of 1-asymmetric donor-acceptor cyclopropane are relatively limited so far.

Method used

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  • 1,3-cyclodiketone enol ether compound, 1-asymmetirc donor-receptor cyclopropane as well as synthesis methods thereof
  • 1,3-cyclodiketone enol ether compound, 1-asymmetirc donor-receptor cyclopropane as well as synthesis methods thereof
  • 1,3-cyclodiketone enol ether compound, 1-asymmetirc donor-receptor cyclopropane as well as synthesis methods thereof

Examples

Experimental program
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preparation example Construction

[0041] The synthesis method includes the following steps: in an organic solvent, using scandium trifluoromethanesulfonate as a catalyst, reacting a 1,3-cyclic diketone compound 1 with a 1-symmetric donor acceptor cyclopropane 2 to obtain a 1,3-cyclic Diketone Enol Ether Compound 3.

[0042] The molar ratio of 1,3-cyclic diketone compound 1 to 1-symmetric donor acceptor cyclopropane 2 is 1.2:1. The molar ratio of 1,3-cyclic diketone compound 1 to scandium trifluoromethanesulfonate is 24 :1 or 12:1. The reaction temperature is 25°C or 45°C; the reaction time is 24 hours.

[0043] The present invention also provides a 1-asymmetric donor acceptor cyclopropane, the structure of the 1-asymmetric donor acceptor cyclopropane 5 is as follows:

[0044]

[0045] Wherein, R is H or methyl; Ar is substituted phenyl, 2-thienyl or 3-(1-tert-butoxycarbonyl)indolyl; n is 0 or 1.

[0046] 1-The synthetic method of asymmetric donor acceptor cyclopropane 5, the synthetic route is:

[0047]...

Embodiment 1

[0050] Embodiment 1: the synthesis of compound 3a (gram level)

[0051]

[0052] Add scandium triflate (0.25mmol ), and the reaction was stirred at room temperature (25° C.) for 24 hours. Then the reaction solution was diluted with dichloromethane and washed with saturated NaHCO 3 solution, the aqueous phase was extracted three times with dichloromethane, all organic phases were combined, washed with saturated brine, NaSO 4Drying, filtration, spin-drying, column chromatography (petroleum ether: ethyl acetate = 2:1-1:1), and rotary evaporation gave 1.74 g of a colorless viscous liquid 3a with a yield of 93%. 1 H NMR (400MHz, CDCl 3 ):δ=1.87-1.97(m,2H,CH 2 ),2.22-2.25(m,2H,CH 2 ),2.30-2.53(m,4H,CH 2 ×2), 3.47(dd, J=6.8Hz, 7.8Hz, 1H, CH), 3.71(s, 3H, CH 3 ),3.72(s,3H,CH 3 ),3.76(s,3H,CH 3 ), 5.03(dd, J=4.9Hz, 8.5Hz, 1H, CH), 5.17(s, 1H, CH), 6.84(d, J=8.7Hz, ArH), 7.15(d, J=8.7Hz, 2H ,ArH)ppm; 13 C NMR (100MHz, CDCl 3 ): δ=20.9, 28.9, 36.5, 36.6, 48.3, 52.6, 52.7, ...

Embodiment 2

[0053] Embodiment 2: the synthesis of compound 3a

[0054] Add scandium triflate (0.0075mmol ), and the reaction was stirred at room temperature (25° C.) for 24 hours. Then the solvent was spin-dried, column chromatography (petroleum ether: ethyl acetate = 2:1-1:1), and rotary evaporation to obtain 51.3 mg of colorless viscous liquid compound 3a with a yield of 91%.

[0055] Compounds 3b, 3c, 3f, 3g, 3i, 3j, 3k, 3l, and 3m similar to 3a in the following examples are all passed through the corresponding 1,3-ring diketone compound 1 and the corresponding compound 1 by the method in Example 2. 1-symmetrical donor-acceptor cyclopropane 2 reaction synthesis. Specifically: in the mixed solution of 1,3-cyclohexanedione compound 1 (0.18mmol) and 1-donor acceptor cyclopropane 2 (0.15mmol) in dichloromethane (1.0mL), add trifluoromethanesulfonic acid scandium (0.0075 mmol), and the reaction was stirred at room temperature (25° C.) for 24 hours. Then spin dry the solvent, perform col...

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Abstract

The invention provides a 1,3-cyclodiketone enol ether compound, a 1-asymmetirc donor-receptor cyclopropane as well as synthesis methods thereof. By use of a reaction method for selectively using oxygen atoms of 1,3-cyclodiketone as nucleophilic sits to perform nucleophilic attack on 1-symmetric donor-receptor cyclopropane, a 1,3-cyclodiketone enol ether compound is obtained; a novel 1-asymmetirc donor-receptor cyclopropane 5 is obtained through intracellular conversion of the compound 3. The 1-asymmetirc donor-receptor cyclopropane 5 is obtained efficiently through desymmetrization of 1-asymmetirc donor-receptor cyclopropane through the simple two-step reaction. Meanwhile, the 1-asymmetirc donor-receptor cyclopropane 5 contains a cycloketene structure which is a very good intermediate module for constructing complex compounds in Domino and multi-component reactions.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to 1,3-cyclic diketone enol ether compounds, 1-asymmetric donor acceptor cyclopropane and their synthesis methods. Background technique [0002] Due to the special reactivity of donor-acceptor cyclopropanes, they are important building blocks for the construction of cyclic and chain-like compounds. The ring-opening reaction of donor-acceptor cyclopropane by nucleophilic attack on carbon atoms has been well developed and has been applied to the synthesis of various cyclic compounds in domino reactions. Heteroatom nucleophilic attack on donor-acceptor cyclopropanes has also been investigated. [0003] Since 1,3-cyclic diketones can be easily isomerized to the enol form, they can be used as both carbon nucleophiles and heteroatom nucleophiles. In fact, in domino or multicomponent reactions, 1,3-cyclic diketones are often used as dinucleophiles, where the C2-position is usua...

Claims

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Application Information

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IPC IPC(8): C07C69/712C07C67/31C07C69/734C07D333/24C07D209/26C07C69/757C07C67/32
CPCC07C69/712C07C69/734C07D333/24C07D209/26C07C69/757C07C67/32C07C2601/02C07C2601/10C07C2601/16C07B2200/07
Inventor 张冬欣陈焱钟俊超蔡虎殷磊满静静张千峰
Owner ANHUI UNIVERSITY OF TECHNOLOGY
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