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Method for preparing beta-carbonyl sulfone compound by using half-sandwich iridium complex

A technology of iridium complexes and carbonyl sulfones, which is applied in the field of preparation of β-carbonyl sulfone compounds, can solve the problems of multi-step preparation of substrates, harsh reaction conditions, and sensitive catalysts, and achieves a simple and green preparation method, mild reaction conditions, and side effects. The effect of less product

Active Publication Date: 2021-07-30
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above methods have different disadvantages, such as harsh reaction conditions, high temperature reaction, sensitive catalyst, instability in air, and multi-step preparation of substrates, etc.

Method used

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  • Method for preparing beta-carbonyl sulfone compound by using half-sandwich iridium complex
  • Method for preparing beta-carbonyl sulfone compound by using half-sandwich iridium complex
  • Method for preparing beta-carbonyl sulfone compound by using half-sandwich iridium complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Synthesis of semi-sandwich iridium complex Ir containing ortho carboryl benzoxazole structure:

[0030]

[0031] At -78°C, n-BuLi (1.6M) n-hexane solution (1.6mmol) was slowly added dropwise to the ortho carborane o-C 2 B 10 h 12 (0.64mmol) in tetrahydrofuran solution, stirred at this temperature for 30 minutes, slowly rose to room temperature and continued to react for 1 hour, then added bromobenzoxazole (0.64mmol), and continued to react at room temperature for 6 hours. Then the binuclear iridium compound [Cp*IrCl 2 ] 2 (256.0 mg, 0.32 mmol) was added to the reaction system for an additional 3 hours. After the reaction, stand and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by column chromatography (volume ratio, petroleum ether / tetrahydrofuran = 6:1), and the red target product is obtained, which is iridium (III) Complex Ir (81% yield).

[0032] 1 H NMR (400MHz, CDCl 3 ,25℃): δ=7.88(d, J=7.0Hz, 1H), 7.72(t, J=...

Embodiment 2

[0035] Synthesis of β-carbonyl sulfone compounds catalyzed by iridium(III) complexes:

[0036]

[0037] The iridium (III) complex prepared in Example 1 was used as a catalyst to catalyze the reaction of acetophenone and benzenesulfonyl chloride: in acetophenone (1 mmol), a trivalent iridium complex (0.001 mmol) in toluene, then add benzenesulfonyl chloride (1mmol) and K 2 CO 3 (1.2mmol), reacted at room temperature for 150 minutes, after the end, the concentrated reaction solution was directly separated by silica gel column chromatography, dried until the mass remained constant, and the corresponding β-carbonyl sulfone compound C 14 h 12 o 3 S (yield 89%), 1 H NMR (CDCl 3 ,500MHz): δ7.95(d,2H,J=8.0Hz),7.90(d,2H,J=7.5Hz),7.67(t,1H,J=7.5Hz),7.60(t,1H,J= 7.0Hz), 7.55(t, 2H, J=7.5Hz), 7.45(t, 2H, J=7.7Hz), 4.77(s, 2H). Elemental analysis: C 64.60, H 4.65 (theoretical); C 64.66, H 4.69 (actual).

Embodiment 3

[0039]Synthesis of β-carbonyl sulfone compounds catalyzed by iridium(III) complexes:

[0040]

[0041] The iridium (III) complex prepared in Example 1 is used as a catalyst to catalyze the reaction of acetophenone and 4-methylbenzenesulfonyl chloride: add trivalent iridium containing an ortho carborane structure to acetophenone (1 mmol) Complex (0.003mmol) in toluene solution, then add 4-methylbenzenesulfonyl chloride (1mmol) and K 2 CO 3 (1.3mmol), react at room temperature for 200 minutes, after the end, the concentrated reaction solution is directly separated by silica gel column chromatography, dried until the mass remains unchanged, and the corresponding β-carbonyl sulfone compound C 15 h 14 OS (93% yield), 1 H NMR (CDCl 3 ,500MHz): δ7.96(dd,2H,J=8.5,1.5Hz),7.78(d,2H,J=8.0Hz),7.65(t,1H,J=7.0Hz),7.49(dd,2H, J=8.0, 7.0Hz), 7.36(d, 2H, J=8.0Hz), 4.75(s, 2H), 2.45(s, 3H). Elemental analysis: C 65.67, H 5.14 (theoretical); C 65.75, H 5.20 (actual).

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Abstract

The invention relates to a method for preparing a beta-carbonyl sulfone compound by using a half-sandwich iridium complex, which comprises the following step: in the presence of alkali, by taking acetophenone and sulfonyl chloride as raw materials and taking the half-sandwich iridium complex containing an o-carboborylbenzoxazole structure as a catalyst, conducting reacting at room temperature to prepare the beta-carbonyl sulfone compound. Compared with the prior art, the method has the advantages that the half-sandwich iridium complex containing the o-carboborylbenzoxazole structure is used as the catalyst, acetophenone and sulfonyl chloride are efficiently catalyzed to react under the room temperature condition to synthesize the beta-carbonyl sulfone compound, the product yield is high, the reaction condition is mild, the substrate is cheap and easy to obtain, and the catalytic efficiency is high.

Description

technical field [0001] The invention belongs to the technical field of preparation of β-carbonyl sulfone compounds, and relates to a method for preparing β-carbonyl sulfone compounds by using a semi-sandwich iridium complex containing an ortho carboryl benzoxazole structure. Background technique [0002] Transition metal-catalyzed carbon-hydrogen bond activation is one of the important methods for constructing carbon-heterobonds in organic synthesis, and is widely used in the synthesis of fine chemical intermediates and natural products. β-carbonyl sulfone compounds are important intermediates in organic synthesis, and they are important raw materials for the synthesis of heterocyclic or alkenyl sulfone compounds, β-hydroxy sulfone, 4-hydropyran and quinoline derivatives. [0003] A variety of methods for the synthesis of β-carbonyl sulfones have been developed, such as the dehalogenation reaction of haloketones and sulfonates (Synth. .1992,33,1131), oxidation of β-hydroxys...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C317/24C07C315/04C07F15/00B01J31/22
CPCC07C315/04C07F15/0033B01J31/2295B01J31/183B01J2231/4294B01J2531/827C07C317/24
Inventor 姚子健王珂高永红刘振江
Owner SHANGHAI INST OF TECH
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