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Triphenylphosphine oxide connecting bisoxazoline ligand, preparation method and application thereof

A technology of triphenylphosphine and bisoxazoline, which is applied in the field of organic synthesis and chiral catalysts to achieve the effects of low reaction temperature, good catalytic activity and good stereoselectivity

Inactive Publication Date: 2012-05-02
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The use of oxazoline ligands combined with triphenylphosphine groups to obtain triphenylphosphine-linked bisoxazoline ligands has not been reported in the literature, so it is necessary to design and synthesize a new type of bifunctional chiral ligand compound

Method used

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  • Triphenylphosphine oxide connecting bisoxazoline ligand, preparation method and application thereof
  • Triphenylphosphine oxide connecting bisoxazoline ligand, preparation method and application thereof
  • Triphenylphosphine oxide connecting bisoxazoline ligand, preparation method and application thereof

Examples

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Effect test

Embodiment 1

[0044] (4S, 4'S)-2,2'-[(phenylphosphorous) two-2,1-phenylene] bis[(4-benzyl)-2-oxazoline] preparation method, The method steps are as follows:

[0045] Under the protection of argon, in a 25ml three-necked flask equipped with a constant pressure dropping funnel and a condenser, add clean and dry magnesium chips (72mg, 3mmol), redistilled THF (2ml) and a small grain of iodine (20mg). At 50°C, a solution of (4S)-4-benzyl-2-(2-bromophenyl)oxazoline (948.6mg, 3mmol) in THF (2ml) was added dropwise; after the addition was complete, reflux for 2 hours, Get the corresponding Grignard reagent. After cooling to room temperature, a solution of phenylphosphoryl dichloride (195 mg, 1 mmol) in THF (2 ml) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. The reaction was quenched with 10 ml of water, and then extracted with dichloromethane (3×10 ml) to separate the liquids. After the obtained organic phase 1 was washed with satu...

Embodiment 2

[0049] (4S, 4'S)-2,2'-[(phenylphosphorous) two-2,1-phenylene] bis[(4-isopropyl)-2-oxazoline] preparation method , the method steps are as follows:

[0050] Under nitrogen protection, in a 25ml three-neck flask equipped with a constant pressure dropping funnel and a condenser, add clean and dry magnesium chips (199mg, 8.29mmol), redistilled THF (2ml) and a small grain of iodine (10mg). At 50°C, a THF (2ml) solution of (4S)-4-isopropyl-2-(2-bromophenyl)oxazoline (2.222mg, 8.29mmol) was added dropwise; hours to obtain the corresponding Grignard reagent. After cooling to room temperature, a solution of phenylphosphoryl dichloride (538 mg, 2.76 mmol) in THF (2 ml) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. The reaction was quenched with 10 ml of water, and then extracted with dichloromethane (3×10 ml) to separate the liquids. After the obtained organic phase 1 was washed with saturated sodium chloride solution an...

Embodiment 3

[0054] (4S, 4'S)-2,2'-[(phenylphosphorous) two-2,1-phenylene] bis[(4-tert-butyl)-2-oxazoline] preparation method , the method steps are as follows:

[0055] Under the protection of nitrogen, in a 25ml three-neck flask equipped with a constant pressure dropping funnel and a condenser, add clean and dry magnesium chips (68mg, 2.85mmol), redistilled THF (2ml) and iodine (30mg). At 50°C, a THF (2ml) solution of (4S)-4-tert-butyl-2-(2-bromophenyl)oxazoline (804.9mg, 2.85mmol) was added dropwise; hours to obtain the corresponding Grignard reagent. After cooling to room temperature, a solution of phenylphosphoryl dichloride (195 mg, 1 mmol) in THF (2 ml) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. The reaction was quenched with 10 ml of water, and then extracted with dichloromethane (3×10 ml) to separate the liquids. After the obtained organic phase 1 was washed with saturated sodium chloride solution and separated,...

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Abstract

The invention discloses a triphenylphosphine oxide connecting bisoxazoline ligand, a preparation method and an application thereof and belongs to the technical field of organic synthesis and chiral catalysts. A structural formula of the triphenylphosphine oxide connecting bisoxazoline ligand provided by the invention is shown as formula I. The variety of the bisoxazoline ligand is increased, and the application of the bisoxazoline ligand in the chiral synthesis technology and other fields is widened. The invention also provides the preparation method for the triphenylphosphine oxide connecting bisoxazoline ligand. According to the preparation method, a derivative of bromophenyl-2-oxazoline or o-bromobenzaldehyde glycol acetal is reacted with magnesium, thereby obtaining a corresponding Grignard reagent, and then the Grignard reagent is reacted with phenylphosphonyl dichloride (PhPOCl2), and after the follow-up treatment is performed, the ligand is obtained. The invention also provides the application of the ligand. The ligand and palladium can be compounded into a chiral bisoxazoline metallic complex compound which is used for catalyzing an asymmetric allyl alkylation reaction.

Description

Technical field [0001] The invention relates to a triphenylphosphine oxide-linked bisoxazoline ligand and its preparation method and application, and belongs to the technical fields of organic synthesis and chiral catalysts. Background technique [0002] Oxazoline and its derivatives are an important class of five-membered heterocyclic compounds containing nitrogen and oxygen, which are widely used in the fields of medicine, pesticides and materials. In recent years, chiral bisoxazolines have become a very important class of chiral ligands in the field of asymmetric catalytic synthesis research due to their structural diversity as ligands, easy availability of chiral sources, and good asymmetric catalytic induction properties. . Further, the chiral bisoxazoline metal complex formed by the chiral bisoxazoline ligand and the transition metal can be used in cyclopropanation reaction, aziridination reaction, allyl substitution reaction, and Diels reaction. -Alder reaction, all...

Claims

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Application Information

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IPC IPC(8): C07F9/653B01J31/24C07B53/00C07C67/343C07C69/618
Inventor 杜大明靳宇
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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