Large-scale preparation method of chiral sulfinamide monophosphine ligand

A technology of sulfinamide mono- and sulfinimide, which is applied in the field of large-scale preparation of chiral sulfinamide monophosphine ligands, can solve the problems of too many organic solvents, unfavorable ligand process production and promotion, etc., to improve the synthesis efficiency effect

Active Publication Date: 2019-12-27
EAST CHINA NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The synthesis route of the ligand is simple, but the purification of the ligand is obtained by column chromatography,

Method used

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  • Large-scale preparation method of chiral sulfinamide monophosphine ligand
  • Large-scale preparation method of chiral sulfinamide monophosphine ligand
  • Large-scale preparation method of chiral sulfinamide monophosphine ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: Large-scale synthesis of chiral sulfinimides

[0025]

[0026] Wherein, THF is tetrahydrofuran; N 2 is nitrogen; Ti(O i Pr) 4 For tetraisopropyl titanate.

[0027] Accurately weigh o-diphenylphosphinebenzaldehyde (52.5mmol) and R-(+)-tert-butylsulfinamide (57.75mmol) in a 500mL three-necked reaction flask, and add 250mL of dry Tetrahydrofuran. Placed at 50° C. for 20 h. After the solvent temperature stabilized, tetraisopropyl titanate (157.5 mmol) was added dropwise through a constant-pressure low-liquid funnel as a condensation agent. After the complete reaction of the raw materials was detected by TLC, 100 mL of ethyl acetate was added to the reaction flask to dilute the solution. Then transfer the reaction solution to a 2L beaker filled with 200mL of saturated saline, and stir it rapidly with a glass rod for 5min to allow the tetraisopropyl titanate to be fully hydrolyzed. Filter, and wash the filter cake with ethyl acetate, transfer the filtrate ...

Embodiment 2

[0029] Embodiment 2: the synthesis of chiral sulfinamide monophosphine ligand

[0030]

[0031] Add imine (40mmol) into a dry 500mL three-necked reaction flask, add 250mL of redistilled tetrahydrofuran under nitrogen atmosphere, and place it at -48°C. After the solution temperature is completely stable, add 80mL of phenyl bromide The magnesium reagent was placed in a constant pressure funnel (80.0 mmol), and the rate of addition was controlled to 2 drops per second. After reacting for 2 hours, turn off the refrigeration and stir overnight, and then continue to stir at room temperature for 2 hours. After the reaction was detected by TLC, 100 mL of saturated ammonium chloride solution was added to quench the reaction. Transfer to a 1L separatory funnel, extract three times with 100mL ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, and concentrate. The crude product was dissolved in 56 mL of acetone, then 40 mL of distilled water was added dropw...

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PUM

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Abstract

The invention discloses a large-scale preparation method of a chiral sulfinamide monophosphine ligand. The method includes condensing chiral sulfinamide and 2-(diphenylphosphino)benzaldehyde which areadopted as raw materials to obtain an intermediate that is chiral sulfinyl imide, and carrying out a nucleophilic addition reaction with a phenylmagnesium bromide reagent to generate the chiral sulfinamide monophosphine ligand. The intermediate imine product and a final product chiral sulfinamide monophosphine ligand are purified by adopting a crystallization method, and column chromatography isnot needed. The method has the characteristics of cheap and accessible raw materials, simple synthesis steps, large-scale synthesis and preparation, a specific three-dimensional structure of the product and the like. The method is mild in condition, and is of important significance for future process and commercialization development of chiral sulfinamide monophosphine ligand products.

Description

technical field [0001] The invention relates to a method for mass preparation of chiral sulfinamide monophosphine ligands, and belongs to the technical field of chemical substances and their synthesis. Background technique [0002] Each configurational isomer of a chiral compound usually exhibits different biological and catalytic activities. Therefore, it is very important to obtain a single chiral configuration isomer compound in organic synthesis. The method of asymmetric catalytic synthesis is currently one of the most effective methods to obtain single chiral isomer compounds. Using a small amount of chiral ligands as catalysts can efficiently and specifically prepare a large number of chiral compounds. It not only reduces the generation of by-product isomers, greatly improves the utilization rate of raw material atoms, but also reduces the pollution to the environment, which is in line with the current concept of green chemistry advocated. In asymmetric synthesis, c...

Claims

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Application Information

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IPC IPC(8): C07F9/50
CPCC07B2200/07C07F9/5022C07F9/5054C07F9/5095
Inventor 肖元晶胡岸靖张展鸣张俊良
Owner EAST CHINA NORMAL UNIV
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