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Planar chiral [2,2]-p-cyclo-aralkyl oxazolinyl phosphine ligand and its synthesis and use

A cycloarylalkyloxazoline bromide compound, a cycloarylalkyloxazoline technology, applied in the field of planar chiral ligands and synthesis, achieving good application prospects, simple methods, and good chemical stability

Inactive Publication Date: 2004-12-22
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the oxazoline phosphine ligands with [2.2] p-arkanes as the backbone have not been reported in the literature so far.

Method used

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  • Planar chiral [2,2]-p-cyclo-aralkyl oxazolinyl phosphine ligand and its synthesis and use
  • Planar chiral [2,2]-p-cyclo-aralkyl oxazolinyl phosphine ligand and its synthesis and use
  • Planar chiral [2,2]-p-cyclo-aralkyl oxazolinyl phosphine ligand and its synthesis and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 uses R=i-CH (CH 3 ) 2 , R' = phenyl compound as an example

[0026] At room temperature, isopropyl substituted (S, 4Rp, 13Sp)-[2.2] p-arylalkyloxazoline bromide (398.0mg, 1.0mmol) was dissolved in ether (15mL) or tetrahydrofuran (15mL) and cooled to -80-20°C, add base (1.0-3.0mmol), react for 1-4 hours, add diphenylphosphine chloride Ph 2 PCl (1.0-3.0mmol), kept at the corresponding temperature for 0.5 hours, raised the temperature to room temperature and continued to react for 12 hours, quenched by adding saturated aqueous ammonium chloride solution, extracted with dichloromethane (2×15mL), washed the organic phase with water, and washed with saturated salt Wash with water, dry over anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify by column chromatography to obtain 357.2 mg of white solid with a yield of 71%.

[0027] P1(S, 4Rp, 13Sp, R=i-CH(CH 3 ) 2 , R'=Ph);

[0028] [α] D 20 =-92.7° (c=0.575, CHCl ...

Embodiment 2

[0123] In a dry reaction tube, add ligand P44 (7.8mg, 0.013mmol), [Pd(C 3 h 5 )Cl] 2 (1.6mg, 0.0044mmol) and toluene (2mL), stirred at room temperature for 0.5h, added 1,3-diphenyl allyl acetate (56.0mg, 0.22mmol), continued complexation for 0.5h, added N, O- Bis(trimethylsilyl)acetamide (BSA) (0.17 mL, 0.69 mmol), dimethyl malonate (0.08 mL, 0.67 mmol), lithium acetate (3 mol%). TLC traced the end of the reaction, added saturated aqueous ammonium chloride solution (5mL), extracted the aqueous phase with dichloromethane (2×10mL), combined the organic phases, dried over anhydrous sodium sulfate, removed the solvent, and purified by column chromatography (petroleum ether: ethyl acetate Ester=7:1), the product is a colorless liquid, 70.6 mg, yield: 98%, 90% ee. 1 H NMR (300MHz, CDCl 3 ): δ3.53(s, 3H), 3.71(s, 3H), 3.96(d, J=11.1Hz, 1H), 4.29(dd, J=10.5, 8.4Hz, 1H), 6.35(dd, J= 15.9, 8.7Hz, 1H), 6.49(d, J=15.9Hz, 1H), 7.18-7.38(m, 10H); MS(EI) m / z(rel) 324(M + , 5), 205(81),...

Embodiment 3

[0125] Add ligand P36 (19.8 mg, 0.025 mmol), Cu(OTf) to a dry reaction tube at room temperature 2 (3.6mg, 0.010mmol) and toluene (2mL), keep the external bath temperature at 30°C, react for 0.5h, add cyclohexenone (48.0mg, 0.5mmol) to continue the reaction for 0.5h. The reaction solution was cooled to -0°C, kept for 15 minutes, diethylzinc (0.75mL, 1.0Minhexane0.75mmol) was added dropwise, after 48 hours of reaction, 1M hydrochloric acid (5mL) was added to quench, and the organic phase was extracted with dichloromethane (2× 10 mL), the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain 59.9 mg of a colorless liquid, yield: 95%. 1 H NMR (300MHz, CDCl 3 ): δ0.92(t, J=7.5Hz, 3H), 1.27-1.46(m, 4H), 1.58-1.77(m, 2H), 1.88-1.98(m, 1H), 2.01-2.10(m, 1H ), 2.22-2.48(m, 3H).

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Abstract

The present invention relates to a kind of planar chiral [2,2]-p-cyclo-aralkyl oxazolinyl phosphine ligand and its synthesis and use. The compound is prepared through the reaction between chiral [2,2]-p-cyclo- oxazolinyl bromide and dibasic phosphine chloride R2'PCl in the presence of alkali. The ligand has two chiral factors of planar chirality and central chirality as well as convertibility of phosphine substituent and oxazolinyl ring substituent, and thus strong adaptability to different asymmetrical catalytic reaction. For example, it has good asymmetrical induction result in Pd catalyzed asymmetrical alloy substituting reaction and copper catalytic asymmetrical 1,4-addition reaction. The ligand has high chemical stability, simple synthesis and is suitable for use in industrial production.

Description

technical field [0001] The invention relates to a class of planar chiral ligands and a synthesis method, in particular to a planar chiral [2.2] p-ring alkane oxazoline phosphine ligand with pseudo-alkaline substitution and a synthesis method. Background technique [0002] Since the late 1990s, the use of planar chiral [2.2]paracyclic aranes as a class of novel chiral ligands in asymmetric catalytic reactions has attracted the attention of chemists, literature and our research The results show that the planar chiral [2.2] paracyclic arane compounds have great application prospects in asymmetric catalytic reactions. [0003] Chiral oxazoline phosphine ligands are an important class of chiral ligands, which are widely used in asymmetric catalytic reactions. For now, such oxazoline phosphine ligands mainly focus on benzene ring or ferrocene derivatives. However, the oxazoline phosphine ligands with [2.2] p-arkanes as the backbone have not been reported in the literature so far...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/24C07F9/653C07F9/6539
Inventor 巫循伟侯雪龙戴立信
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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