Modular synthesis method of polysubstituted trifluoromethyl allene

A technology of trifluoromethyl allene and trifluoromethyl, applied in chemical instruments and methods, preparation of organic compounds, steroids, etc., to achieve strong compatibility, low-cost synthesis, and mild reaction conditions

Active Publication Date: 2022-05-27
WUHAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, most of the current methods for synthesizing trifluoromethyl-substituted allenes have major

Method used

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  • Modular synthesis method of polysubstituted trifluoromethyl allene
  • Modular synthesis method of polysubstituted trifluoromethyl allene
  • Modular synthesis method of polysubstituted trifluoromethyl allene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024]

[0025] Under an inert (argon) atmosphere, sodium decapolytungstate (13.3 mg, 0.004 mmol), (4,4'-di-tert-butyl-2,2'-bipyridine) was added to the reaction tube containing the magnetron. Nickel dibromide (9.8 mg, 0.02 mmol), potassium phosphate (84.8 mg, 0.4 mmol), 1,3-enyne compound 1a (47.1 mg, 0.24 mmol), 4-bromoethyl benzoate 2a (45.8 mg, 0.2 mmol), cyclohexane 3a (168.0 mg, 2 mmol) and acetone (0.5 mL). The reaction was carried out under the irradiation of a violet lamp (10w, 390nm) at room temperature for 12 hours, concentrated, and subjected to flash column chromatography to obtain the product 4 (71.9mg, 84% yield) as a colorless liquid.

[0026] 1 H NMR (600MHz, CDCl 3 )δ8.05(d,J=8.4Hz,2H),7.43-7.34(m,5H),7.31-7.28(m,2H),4.40(q,J=7.1Hz,2H),2.22(d,J =7.1Hz, 2H), 1.74-1.67(m, 2H), 1.64-1.60(m, 3H), 1.57-1.50(m, 1H), 1.40(t, J=7.1Hz, 3H), 1.19-1.08( m,3H),0.94-0.85(m,2H); 13 C NMR (151MHz, CDCl 3 )δ204.4(q,J=4.1Hz),166.2,139.7,134.3,130.1,129.8,128.7,128.5,...

Embodiment 2

[0028]

[0029] In an inert atmosphere, sodium decapolytungstate (13.3 mg, 0.004 mmol), (4,4'-di-tert-butyl-2,2'-bipyridine) nickel dibromide was added to the reaction tube containing the magnetron. (9.8 mg, 0.02 mmol), potassium phosphate (84.8 mg, 0.4 mmol), 1,3-enyne compound 1b (54.3 mg, 0.24 mmol), 4-bromoethyl benzoate 2a (45.8 mg, 0.2 mmol), Cyclohexane 3a (168.0 mg, 2 mmol) and acetone (0.5 mL). Under the irradiation of a violet lamp (10w, 390nm), the reaction was carried out at room temperature for 12 hours, concentrated, and subjected to flash column chromatography to obtain the product 5 (58.6 mg, 64% yield) as a colorless liquid.

[0030] 1 H NMR (600MHz, CDCl 3 )δ8.04(d,J=8.4Hz,2H),7.39(d,J=8.4Hz,2H),7.22(d,J=8.8Hz,2H), 6.91(d,J=8.8Hz,2H) ,4.39(q,J=7.1Hz,2H),3.83(s,3H),2.24-2.16(m,2H),1.74-1.67(m,2H),1.65-1.58(m,3H),1.57-1.49 (m, 1H), 1.40 (t, J=7.1Hz, 3H), 1.22-1.08 (m, 3H), 0.95-0.84 (m, 2H); 13 C NMR (151MHz, CDCl 3 )δ204.4(q,J=4.1Hz),166.4,159.9,140.2...

Embodiment 3

[0032]

[0033] In an inert atmosphere, sodium decapolytungstate (13.3 mg, 0.004 mmol), (4,4'-di-tert-butyl-2,2'-bipyridine) nickel dibromide was added to the reaction tube containing the magnetron. (9.8 mg, 0.02 mmol), potassium phosphate (84.8 mg, 0.4 mmol), 1,3-enyne compound 1c (53.1 mg, 0.24 mmol), 4-bromoethyl benzoate 2a (45.8 mg, 0.2 mmol), Cyclohexane 3a (168.0 mg, 2 mmol) and acetone (0.5 mL). Under the irradiation of a violet lamp (10w, 390nm), the reaction was carried out at room temperature for 12 hours, concentrated, and subjected to flash column chromatography to obtain 6 (22.3 mg, 25% yield) as a colorless liquid product.

[0034] 1 H NMR (600MHz, CDCl 3 )δ8.07(d,J=8.3Hz,2H),7.67(d,J=8.3Hz,2H),7.40(d,J=8.4Hz,2H), 7.34(d,J=8.4Hz,2H) ,4.40(q,J=7.1Hz,2H),2.23(d,J=7.1Hz,2H),1.65-1.60(m,5H),1.54-1.49(m,1H), 1.40(t,J=7.1 Hz,3H),1.16-1.08(m,3H),0.92-0.85(m,2H); 13 C NMR (151MHz, CDCl 3 )δ204.9(q,J=4.2 Hz),166.0,139.4,138.4,132.6,130.7,130.2,129.0,128.4,123.4(q,...

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Abstract

The invention discloses a method for modularly synthesizing polysubstituted trifluoromethyl allene, and belongs to the technical field of organic synthesis. According to the method, a 2-trifluoromethyl-1, 3-enyne compound, an electrophilic reagent (including but not limited to aryl bromide, alkenyl bromide, alkynyl bromide and acyl chloride) and a hydrocarbon are taken as raw materials, and 1, 2-difluoro-1, 3-enyne of the 2-trifluoromethyl-1, 3-enyne is realized under irradiation of purple light through concerted catalysis of decatungstate and a metal nickel complex. And 2, 4-bifunctionalization is carried out, such that polysubstituted trifluoromethyl allene is obtained. According to the method disclosed by the invention, various functionalized polysubstituted trifluoromethyl allene compounds are economically and efficiently prepared from simple raw materials under the synergistic catalysis of the cheap photocatalyst and nickel catalyst.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for modular synthesis of polysubstituted trifluoromethyl allenes. Background technique [0002] Allenyl group is an important structural unit in the structure of natural products, and it is also an important organic synthesis intermediate that can be widely transformed, and the introduction of trifluoromethyl group can significantly affect the physicochemical properties and biological activities of organic molecules. Therefore, the development of synthetic trifluoromethyl group The methodology of methyl-substituted allene structures has important research significance. [0003] However, most of the current methods for synthesizing trifluoromethyl-substituted allenes have major problems in terms of substrate scope, functional group compatibility, and availability of raw materials. SUMMARY OF THE INVENTION [0004] The purpose of the present invent...

Claims

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Application Information

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IPC IPC(8): C07C67/343
CPCC07C67/343C07C253/30C07F7/1892C07F5/025C07C231/12C07C45/455C07F7/0827C07D209/48C07J1/0011C07D493/14C07D311/72C07D213/64C07D333/54C07D333/76C07D209/86C07D307/91C07D307/88C07D493/04C07D333/22C07D307/46C07D307/16C07D317/60C07D319/12C07D309/08C07D405/06C07C2601/14C07C2601/08C07C2602/28C07C2602/24C07C2601/18C07C2603/74C07C69/76C07C69/94C07C255/57C07C69/753C07C69/65C07C69/734C07C69/738C07C233/66C07C49/84C07C49/813C07C69/92
Inventor 孔望清刘文峰刘楚晗
Owner WUHAN UNIV
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