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Derivative of 2-trifluoromethyl cyclopentanone and preparation method thereof

A technology for trifluoromethylcyclopentanone and trifluoromethylation, which is applied in the field of derivatives of 2-trifluoromethylcyclopentanone and their preparation, can solve problems such as unsatisfactory free radical regioselectivity, and achieves The effect of overcoming unsatisfactory regioselectivity, good application prospects and mild reaction conditions

Pending Publication Date: 2022-02-18
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 of 2-trifluoromethyl cyclopentanone and preparation method thereof
  • Derivative of 2-trifluoromethyl cyclopentanone and preparation method thereof
  • Derivative of 2-trifluoromethyl cyclopentanone and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Add CF sequentially to the dry reaction tube 3 SO 2 Na (62.4mg, 0.4mmol), 4CzIPN (3.2mg, 0.02mmol), after vacuuming and changing nitrogen three times, add acetylene derivative II-a (37.2mg ,0.2mmol). After the system was reacted at room temperature for 18 hours, water was added to the reaction system to quench the reaction, and 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. The solvent was spin-dried, and the column Chromatography was carried out to separate petroleum ethers / EtOAc=40:1 to obtain white solid I-a, yield: 81%, dr>20:1, 1 HNMR (600MHz, CDCl 3 )δ10.04(s,1H),7.91(d,J=8.2Hz,2H),7.40(d,J=8.2Hz,2H),3.54-3.44(m,2H),2.49(s,2H), 1.20(s,3H),0.81(s,3H). 13 C NMR (151MHz, CDCl 3 )δ206.02, 191.60, 142.83, 135.80, 129.70, 129.02, 124.43 (q, J=279.6Hz), 54.88, 54.48, 54.22 (q, J=26.6Hz), 38.40, 27.01, 22.85. 19 F NMR (565MHz, CDCl ...

Embodiment 2

[0043] Except that the acetylenic ketone shown in the structural formula II-b is used to replace the acetylenic ketone shown in the structural formula II-b in Example 1 and the reaction time is 28 hours, all the other operating steps are the same as in Example 1, and the white solid I-b is obtained by separation, the yield: 72% yield, dr>20:1. Product spectrum analysis: 1 H NMR (600MHz, CDCl 3 )δ7.35(d, J=8.4Hz, 2H), 7.14(d, J=8.4Hz, 2H), 3.38(dq, J=12.2,8.6Hz, 1H), 3.33(d, J=12.4Hz, 1H), 2.45(s, 2H), 1.16(s, 3H), 0.78(s, 3H). 13 C NMR (151MHz, CDCl 3 )δ206.51, 134.27, 133.44, 129.58, 128.57, 124.51 (q, J=279.4Hz), 54.88, 54.18 (q, J=26.3Hz), 53.21, 38.13, 26.90, 22.73. 19 F NMR (565MHz, CDCl 3 )δ-66.23.HRMS(ESI)m / z:[M+H] + Calcd for C 14 h 14 BrF 3 O+H + :335.0253; Found 335.0255.

[0044] The reaction formula is as follows:

[0045]

Embodiment 3

[0047] Except that the acetylenic ketone shown in the structural formula II-c is used to replace the acetylenic ketone shown in the structural formula II-c in Example 1 and the reaction time is 28 hours, all the other operating steps are the same as in Example 1, and the white solid I-c is obtained by separation, the yield: 72% yield, dr>20:1. Product spectrum analysis: 1 H NMR (600MHz, CDCl 3 )δ7.52-7.49(m,2H),7.12-7.06(m,2H),3.41-3.31(m,2H),2.45(s,2H),1.16(s,3H),0.78(s,3H) . 13 C NMR (151MHz, CDCl 3 )δ206.49, 134.27, 133.45, 129.58, 128.57, 124.51(q, J=279.5Hz), 54.88(q, J=1.0Hz), 54.24(q, J=26.4Hz), 53.21(q, J=0.9Hz) ,38.13,26.91,22.73. 19 F NMR (565MHz, CDCl 3 )δ-66.22.HRMS(ESI)m / z:[M+H] + Calcd for C 14 h 14 CIF 3 O+H + :291.0758.

[0048] The reaction formula is as follows:

[0049]

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Abstract

The invention discloses a 2-trifluoromethyl cyclopentenone derivative and a preparation method of the 2-trifluoromethyl cyclopentenone derivative. The preparation method comprises the following steps: adding a photocatalyst and a trifluororeagent into N,N-dimethylformamide, then adding the reactant into an acetylenic ketone compound with a structure as shown in a formula II, and forming a reaction system in a certain reaction environment; and after the reaction is completed, performing post-treatment to obtain the 2-trifluoromethyl cyclopentanone derivative with the structure shown in the formula I in the claim 1. According to the ingenious design, carbonyl is used as a guiding group, a trifluoromethyl free radical region is selectively added to internal alkyne, and then hydrogen migration, 5-internal cyclization, electron transfer and proton transfer are carried out to start the reaction. Besides, the reaction condition is mild, the substrate application range is wide and the operation is simple. A new way is provided for synthesis of the complex 2-trifluoromethyl cyclopentanone derivative.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a derivative of 2-trifluoromethylcyclopentanone and a preparation method thereof. Background technique [0002] As a five-membered heterocyclic compound containing a carbonyl group, cyclopentanone has been widely used as an intermediate in the fields of spices, medicine, and pesticides, and can be used in the synthesis of new spices, anti-inflammatory and anti-cancer drugs, insecticides, and herbicides middle. In addition, various natural and non-natural medicines also contain this fragment. Prostaglandin D2 (PGD2) is a biologically active prostaglandin that participates in many important physiological processes. [0003] [0004] The common synthesis method of cyclopentanone is the study of adipic acid or adipic acid ester derivatives undergoing intramolecular condensation at high temperature in the presence of a catalyst to generate cyclopentanone. However, th...

Claims

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Application Information

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IPC IPC(8): C07C69/712C07C67/307C07D207/16C07D327/04C07C49/583C07C45/68C07C49/567
CPCC07C69/712C07C67/307C07D207/16C07D327/04C07C49/583C07C45/68C07C49/567C07B2200/07C07C2601/08
Inventor 罗芳勒思雅张芳苏静雯
Owner ZHEJIANG NORMAL UNIVERSITY
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