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Derivative containing 2-trifluoromethyl cyclopentenone and preparation method of derivative

A technology for trifluoromethyl cyclopentenone and derivatives, which is applied in the field of derivatives containing 2-trifluoromethyl cyclopentenone and their preparation, can solve the problems of unsatisfactory free radical regioselectivity and the like, and achieves overcoming The effects of unsatisfactory regioselectivity, mild reaction conditions, and simple operation

Pending Publication Date: 2022-02-01
ZHEJIANG NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In contrast, the 5-endo cyclization initiated by the addition of intermolecular radicals to internal alkynes to form endocyclic compounds remains a great challenge due to the suboptimal regioselectivity of radicals for internal alkyne addition.

Method used

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  • Derivative containing 2-trifluoromethyl cyclopentenone and preparation method of derivative
  • Derivative containing 2-trifluoromethyl cyclopentenone and preparation method of derivative
  • Derivative containing 2-trifluoromethyl cyclopentenone and preparation method of derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] CuCN (1.8mg, 0.02mmol), Togni reagent (94.8mg, 0.3mmol) and K 2 CO 3 (55.3mg, 0.4mmol), after vacuuming and changing nitrogen three times, add II-1 fenofibrate acetylene derivative (37.2mg, 0.2mmol) dissolved in 2mL of ethyl acetate acetonitrile. After the system was reacted at 50°C for 10 hours, water was added to the reaction system to quench the reaction, the reaction was extracted three times with ethyl acetate, the organic phases were combined, washed with saturated sodium chloride solution and dried with anhydrous sodium sulfate, and the solvent was spin-dried. Column chromatography was used to separate petroleum ethers / EtOAc=10:1 to obtain white solid I-1, yield: 56%; 1 H NMR (600MHz, CDCl 3 )δ7.83(d, J=8.2Hz, 2H), 7.79(d, J=8.8Hz, 2H), 7.27-7.23(m, 2H), 6.91-6.87(m, 2H), 5.13-5.06(m ,1H),2.62(s,2H),1.68(s,6H),1.29(s,6H),1.21(d,J=6.3Hz,6H). 13 C NMR (151MHz, CDCl 3 )δ200.07, 194.61, 173.07, 159.92, 138.55, 136.05, 132.09, 130.25 (q, J=31.2Hz), 130.01, 129.77...

Embodiment 2

[0040] Except that the amino acid acetylenone derivative shown in structural formula II-2 is used to replace the fenofibrate acetylenic ketone derivative shown in the structural formula in Example II-3, the rest of the operating steps are the same as in Example 1, and the white solid I is separated and obtained -2, yield: 80%, mp127-129°C, dr=1.3:1; petroleum ethers / EtOAc=5:1; 1 H NMR (600MHz, CDCl 3 )δ8.11(d, J=8.2Hz, 2H), 7.27-7.23(m, 2H), 5.60-5.56(m, 1H), 4.55(t, J=7.9Hz, 0.43H, minorrotamer), 4.45( t,J=8.0Hz,0.57H,major rotamer),3.87(d,J=3.1Hz,1H),3.80(s,1.29H,minor rotamer),3.79(s,1.71H,major rotamer),3.75- 3.73(m,1H),2.62(s,1H),2.60-2.53(m,2H),2.40-2.35(m,1H),1.48(s,3.90H,minor rotamer),1.46(s,5.10H, major rotamer), 1.28(s,6H). 13 C NMR (151MHz, CDCl 3 )δ199.87, 183.63, 173.01, 165.11, 153.60, 137.47, 130.29 (q, J=31.5Hz), 130.16, 129.44, 120.66 (q, J=273.4Hz), 80.73, 72.98, 57.99, 53.37, 52.8075, 5 ,36.70,28.24,26.60. 19 F NMR (565MHz, CDCl 3 )δ-60.38.HRMS(ESI)m...

Embodiment 3

[0044] Except that the fenofibrate acetylenone derivative shown in the structural formula I-1 in Example 1 is replaced by the clofibrate acetylenic ketone derivative shown in the structural formula II-3, the remaining operating steps are the same as in Example 1, and the separation is obtained Yellow liquid I-3, yield: 81%, petroleum ethers / EtOAc=10:1; 1 H NMR (600MHz, CDCl 3 )δ7.02(d, J=8.7Hz, 2H), 6.88(d, J=8.7Hz, 2H), 4.23(q, J=7.1Hz, 2H), 2.55(s, 2H), 1.64(s, 6H), 1.24(s, 6H), 1.21(t, J=7.1Hz, 3H). 13 C NMR (151MHz, CDCl 3 )δ200.58, 185.51, 173.91, 156.31, 129.77 (q, J=30.7Hz), 127.44, 125.69, 120.95 (q, J=273.4Hz), 118.02, 79.34, 61.55, 51.13, 43.07, 26.75, 235.974.1 19 F NMR (565MHz, CDCl 3 )δ-60.35.HRMS(ESI)m / z:[M+H] + Calcd for C 20 h 23 f 3 o 4 +H + :385.1621; Found 385.1626.

[0045] The reaction formula is as follows:

[0046]

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Abstract

The invention discloses a 2-trifluoromethyl-containing cyclopentenone derivative with a structure shown in a formula I and a preparation method of the 2-trifluoromethyl-containing cyclopentenone derivative. Copper cyanide, a Togni reagent, potassium carbonate and an acetylenic ketone compound are added into a reaction system, the reaction system is formed in a certain reaction environment, and after the reaction is completed, post-treatment is performed to obtain the 2-trifluoromethyl-containing cyclopentenone derivative. According to the method, carbonyl is adopted as a guiding group, a cyclopentenone ring skeleton structure is synthesized on the basis of a free radical tandem cyclization reaction strategy, construction of a series of complex 2-trifluoromethyl cyclopentenone is efficiently achieved, the reaction yield is medium to good, operation is easy, and a new way is provided for synthesis of cyclopentenone compounds.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to derivatives containing 2-trifluoromethyl cyclopentenone and a preparation method thereof. Background technique [0002] As a five-membered heterocyclic compound containing both carbon-carbon double bonds and carbon-oxygen double bonds, cyclopentenone has been widely used in the fields of spices, materials, and medicine. Many natural and non-natural molecules with physiological or pharmacological activities contain this fragment. The diterpene pepluanol B of Euphorbiaceae has cytotoxicity, antiviral, reverse multidrug resistance and antitumor activities. A branch of artemisinic acid Rupestonic acid can inhibit influenza virus. [0003] [0004] Traditional cyclopentenone synthesis methods are usually carried out by Pauson-Khand reaction (PKR) or Nazarov cyclization. In 1973, I.U.Khand and P.L.Pauson reported the reaction of various alkyne cobalt hexacarbonylate complexes wit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/712C07C67/30C07C67/58C07C67/56C07D207/16C07D493/04C07D311/72C07J9/00
CPCC07C69/712C07C67/30C07C67/58C07C67/56C07D207/16C07D493/04C07D311/72C07J9/00C07C2601/10
Inventor 朱钢国勒思雅邱佳燕张芳
Owner ZHEJIANG NORMAL UNIVERSITY
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