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Biphenyl ligand, synthetic method thereof and application thereof in methoxyl carbonylation reaction of racemized propargyl alcohol carbonate

A technology of propargyl carbonate and biphenyl ligands, which is applied in the direction of carbon monoxide or formate reaction preparation, asymmetric synthesis, organic chemical methods, etc., and can solve the problem that the response time is more than 48 hours and the universal range of substrates is narrow , harsh reaction conditions and other issues, to achieve the effect of increased enantioselectivity, faster reaction rate, and good reactivity

Active Publication Date: 2014-10-22
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are equivalent chiral reagents used in the above methods, such as using chiral raw materials or using equivalent chiral catalysts; the universal scope of substrates is very narrow, and most of the reports only involve one or two chiral 2,3- Synthesis of allenoic acid esters; long reaction time, for example, the reaction time is more than 48 hours; the reaction conditions are harsh, requiring extremely low temperature, for example, minus 50°C and the reaction needs to be carried out under high pressure, for example, pressurization to 200psi is required And other issues

Method used

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  • Biphenyl ligand, synthetic method thereof and application thereof in methoxyl carbonylation reaction of racemized propargyl alcohol carbonate
  • Biphenyl ligand, synthetic method thereof and application thereof in methoxyl carbonylation reaction of racemized propargyl alcohol carbonate
  • Biphenyl ligand, synthetic method thereof and application thereof in methoxyl carbonylation reaction of racemized propargyl alcohol carbonate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1R-(+)-2,2'-bis(dichlorophosphinoxy)-6,6'-dimethoxy-1,1'-biphenyl (wyl-13-137)

[0032]

[0033] Add R-(+)-2,2'-bis(diethoxyphosphinoxy)-6,6'-dimethoxy-1,1'-biphenyl (2.4309g, 5mmol) in turn to the one-necked bottle , N,N'-dimethylformamide (0.5mL) and thionyl chloride (5mL), the single-necked bottle was placed in an oil bath at 90°C and heated to reflux for 9.8 hours. After the reaction system was cooled to room temperature, a large amount of thionyl chloride was pumped away with a water pump, and then the crude product was pumped dry with an oil pump to obtain 2.1731 g of a tan solid, with a crude yield of 97%. The resulting crude product was directly used in the next step.

[0034] 1 H NMR (300MHz, CDCl 3 )δ7.73-7.68 (m, 1H, ArH), 7.66-7.54 (m, 3H, ArH), 7.27-7.20 (m, 2H, ArH), 3.78 (s, 6H, 2x CH 3 ); 31 P NMR (121MHz, CDCl 3 )δ33.97.

Embodiment 2

[0035] Example 2R-(+)-2,2'bis(bis(3,5-dimethoxyphenyl)phosphineoxy)-6,6'-dimethoxy-1,1'-biphenyl ( wyl-13-139)

[0036]

[0037] Under the protection of argon, put magnesium chips (264.5 mg, 11 mmol) into a dry three-necked bottle, vacuumize and bake with a heat gun at the same time, and replace the bottle with argon atmosphere after cooling. Add freshly distilled tetrahydrofuran (15 mL) and a grain of iodine into the reaction flask, and stir at room temperature. 3,5-Dimethoxybromobenzene (2.1708g, 10mmol) was completely dissolved in freshly distilled tetrahydrofuran (5mL), and the solution was dropped into a three-neck flask within 15 minutes, stirred at room temperature for 2 hours, and set aside.

[0038] Under the protection of argon, add the R-(+)-2,2'bis(dichlorophosphinyloxy)-6,6'-dimethoxy-1,1 prepared in Example 1 into a dry three-neck flask '-biphenyl (448.2 mg, 1 mmol) and freshly distilled tetrahydrofuran (20 mL). Place the reaction bottle in a -78°C cold bat...

Embodiment 3

[0040] Example 3R-(+)-2,2'-bis(bis(3,5-dimethoxyphenyl)phosphine)-6,6'-dimethoxy-1,1'-biphenyl (wyl -13-143)

[0041]

[0042] Under argon protection, add the R-(+)-2,2' bis(bis(3,5-dimethoxyphenyl) Phosphinoxy)-6,6'-dimethoxy-1,1'-biphenyl (598.9 mg, 0.7 mmol) and freshly distilled toluene (20 mL). After stirring at room temperature, tri-n-butylamine (1.7 mL, d=0.778, 1.3226 g, 7 mmol) and trichlorosilane (0.7 mL, d=1.347, 942.9 mg, 7 mmol) were added successively. The reaction was heated to reflux at 130°C and stirred for 9 hours. Then the reaction was cooled to 0°C, and degassed 20% sodium hydroxide aqueous solution was slowly added to the reaction to quench the reaction (80mL), extracted with ethyl acetate (80mL x3), and the organic phases were combined and washed with water and saturated brine successively (80 mL each), dried over anhydrous sodium sulfate, filtered, concentrated, and 385.9 mg of a white solid product can be obtained by flash column chromatography, w...

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Abstract

The invention discloses a biphenyl ligand, a synthetic method thereof and an application thereof in an asymmetric methoxyl carbonylation reaction, catalyzed by palladium, of racemized propargyl alcohol carbonate, wherein the biphenyl ligand is R-(+)-2,2'-bis(di(3,5,dimethoxyphenyl)-6,6'-dimethoxy-1,1'-biphenyl. The biphenyl can achieve asymmetric induction to the methoxyl carbonylation reaction of the racemized propargyl alcohol carbonate and 2,3-allenoate having higher optical purity can be prepared in high efficiency.

Description

technical field [0001] The invention relates to a biphenyl ligand and its synthesis method, as well as its application in the asymmetric methoxycarbonylation reaction of palladium-catalyzed racemic propargyl alcohol carbonate. Background technique [0002] Chiral phosphine ligands play a very important role in the study of asymmetric reactions catalyzed by transition metals, and chiral biphenyl bisphosphine ligands with atropisomerism are important components of chiral phosphine ligands. . The design and synthesis of chiral biphenyl bisphosphine ligands has always been an important research topic. The Schmid group reported the first chiral biphenyl-based bisphosphine ligand—R-(+)-2,2′-bisdiphenylphosphine-6,6′-dimethoxy-1,1′- In the synthesis of biphenyl, they used the ligand to form a stable complex with palladium, and determined the structure and configuration of the ligand by determining the single crystal structure of the complex, and then successfully applied it to rh...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50C07B53/00C07C67/36C07C69/65C07C69/618C07C69/587
Inventor 麻生明王玉立
Owner EAST CHINA NORMAL UNIV
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