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A kind of rhodium-catalyzed carbon-hydrogen activation reaction synthesizes the method for the isoindol-1-one analog of acyl silicon substitution

A technology of hydrocarbon activation and acyl silicon, applied in the field of isoindol-1-one analogs, can solve the problems of limiting the synthesis range of acyl silane, harsh reaction conditions, uneconomical and the like, and achieves the effect of wide substrate applicability

Active Publication Date: 2022-05-17
SICHUAN UNIV
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Problems solved by technology

Although the synthesis of acylsilanes has been reported, the traditional linear synthesis method is neither economical nor faced with the problem of harsh reaction conditions, which may limit the scope of synthesis of acylsilanes, especially those highly functional synthetic methods

Method used

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  • A kind of rhodium-catalyzed carbon-hydrogen activation reaction synthesizes the method for the isoindol-1-one analog of acyl silicon substitution
  • A kind of rhodium-catalyzed carbon-hydrogen activation reaction synthesizes the method for the isoindol-1-one analog of acyl silicon substitution
  • A kind of rhodium-catalyzed carbon-hydrogen activation reaction synthesizes the method for the isoindol-1-one analog of acyl silicon substitution

Examples

Experimental program
Comparison scheme
Effect test

Embodiment example 1

[0020] Implementation Case 1: Synthesis of Compound 1

[0021]

[0022] Under the condition of argon, add in sequence in a clean pressure-resistant bottle N -Substituted benzamide (21.1mg, 0.1mmol), 1-(tert-butyldimethylsilyl)prop-2-en-1-one (51mg, 0.3mmol), dichloro(pentamethylcyclopentyl Dienyl) rhodium (Ⅲ) (3.1mg, 0.005mmol), silver carbonate (55.2mg, 0.2mmol), acetonitrile (1.5ml), placed in an oil bath at 100°C and stirred for 36h.

[0023] After the reaction, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography to obtain the product, namely a light yellow solid with a melting point range of 150.5-151.7° C. and a yield of 83%. 1 H NMR (400 MHz, Chloroform- d ) δ 7.79 (d, J = 7.8Hz, 1H), 7.55 (d, J = 7.4 Hz, 2H), 7.44 – 7.38 (m, 2H), 7.29 (d, J = 7.8 Hz,1H), 7.20 (t, J = 7.4 Hz, 1H), 7.17 (s, 1H), 5.82 (dd, J = 8.4, 3.2 Hz, 1H),3.13 (dd, J = 18.6, 3.2 Hz, 1H), 2.82 (dd, J = 18.6, 8.5 Hz, 1H), 2....

Embodiment example 2

[0024] Implementation Case 2: Synthesis of Compound 2

[0025]

[0026] Under the condition of argon, add in sequence in a clean pressure-proof bottle N -Substituted benzamide (27.5mg, 0.1mmol), 1-(tert-butyldimethylsilyl)prop-2-en-1-one (51mg, 0.3mmol), bis(hexafluoroantimonate)tri Acetonitrile (pentamethylcyclopentadienyl) rhodium (III)) (8.3mg, 0.01mmol), silver carbonate (55.2mg, 0.2mmol), acetonitrile (1.5ml), placed in a 100°C oil bath and stirred for 36h.

[0027] After the reaction, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography to obtain the product, that is, a light yellow solid with a melting point range of 169.5-171.3° C. and a yield of 75%. 1 H NMR (400 MHz, Chloroform- d ) δ 7.77 (d, J = 8.1Hz, 1H), 7.63 (dd, J = 8.1, 1.7 Hz, 1H), 7.56 (s, 1H), 7.52 (dd, J = 8.7, 1.2Hz, 2H), 7.45 – 7.40 (m, 2H), 7.26 – 7.20 (m, 1H), 5.81 (dd, J = 8.6, 3.1 Hz,1H), 3.16 (dd, J = 18.7, 3.2 Hz, 1H), 2.81...

Embodiment example 3

[0028] Implementation Case 3: Synthesis of Compound 3

[0029]

[0030] Under the condition of argon, add in sequence in a clean pressure-resistant bottle N-Substituted benzamide (22.7mg, 0.1mmol), 1-(tert-butyldimethylsilyl)prop-2-en-1-one (51mg, 0.3mmol), dichloro(pentamethylcyclopentyl Dienyl) rhodium (Ⅲ) (6.2mg, 0.01mmol), silver acetate (33.4mg, 0.2mmol), tetrahydrofuran (1.5ml), placed in an oil bath at 100°C and stirred for 36h.

[0031] After the reaction, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography to obtain the product, a light yellow solid with a melting point range of 94.9-96.3°C and a yield of 55%. 1 H NMR (400 MHz, Chloroform- d ) δ 7.89 (d, J = 7.0 Hz,1H), 7.54 (td, J = 7.4, 1.4 Hz, 1H), 7.50 – 7.44 (m, 1H), 7.43 – 7.39 (m,2H), 7.37 (d, J = 6.4 Hz, 1H), 6.98 – 6.91 (m, 2H), 5.76 (dd, J = 8.2, 3.6Hz, 1H), 3.82 (s, 3H), 3.12 (dd, J = 18.6, 3.6 Hz, 1H), 2.80 (dd, J = 18.6,8.2 Hz, ...

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Abstract

The invention discloses a method for synthesizing acyl silicon-substituted isoindol-1-one compounds through a rhodium-catalyzed carbon-hydrogen activation reaction. The present invention uses N-substituted benzamide and α, β-unsaturated acyl silicon as raw materials, and with the assistance of additives, through a carbon-hydrogen activation reaction catalyzed by a transition metal, efficiently constructs acyl silicon-substituted isoindol-1-one structure. This method avoids the problems of low economy and harsh reaction conditions of the traditional linear synthesis method. It is a simple and mild method to replace the traditional synthesis of acylsilanes, and it has wide substrate applicability and broad application prospects.

Description

technical field [0001] The invention relates to a new method for constructing acyl silicon-substituted isoindol-1-one analogues through rhodium-catalyzed C-H activation reaction of N-substituted benzamide and α, β-unsaturated acyl silicon, belonging to the technical field of organic chemistry . Background technique [0002] C-H bond activation has always been one of the research hotspots in organic chemical synthesis. C-H bond activation is a process in which the C-H at the reaction site coordinates with the metal center with the assistance of the directing group to form a relatively stable five-membered or six-membered ring metal intermediate, thereby selectively activating the intramolecular C-H bond. . Due to its high atom economy, broad substrate range, and mild reaction conditions, it has gradually become the most attractive strategy for constructing C-C bonds and C-heterobonds. 1 Among them, rhodium catalysts stand out in the field of C–C coupling reactions via C–H ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F7/10
CPCC07F7/083C07F7/0812Y02P20/584
Inventor 吴勇海俐杨增豹李江联周荟
Owner SICHUAN UNIV
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