Preparation method and application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof

A metal complex and oxazoline technology, which is applied in the field of preparation of chiral phosphine-oxazoline ligand ionic complexes, can solve the problems of substrate limitation and single electronic effect of the skeleton

Inactive Publication Date: 2013-01-16
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the types of monophosphine ligands are far less than those of bisphosphine ligands at present, and the skeleton, dihedral angle, and electronic effe

Method used

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  • Preparation method and application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof
  • Preparation method and application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof
  • Preparation method and application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0064] Example 1: Preparation of (R)-[6,6'-(S,S)-2,3-butanedioloxy)]-2,2'-dihydroxybiphenyl

[0065] Under nitrogen protection, suspend 0.88 g (4.04 mmol) of 2,2',6,6'-tetrahydroxybiphenyl 1, 3.06 g (9.39 mmol) of cesium carbonate in 120 mL of dry N,N-dimethylformamide (DMF), the temperature was raised to 80°C, and stirred for 1 hour. Then 1.0 g (4.06 mmol) of (2R,3R)-2,3-butanediol methanesulfonate was dissolved in 40 mL of dry DMF, and slowly added dropwise to the suspension of 1 and cesium carbonate within 4 hours middle. The suspension was stirred at 80°C for 12 hours, and DMF was evaporated under reduced pressure. The reaction residue was poured into 1mol / L hydrochloric acid, extracted 3 times with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by column chromatography to obtain 0.57g product (R)-[ 6,6'-((S,S)-2,3-butanedioloxy)]-2,2'-dihydroxybiphenyl, yield 52%.

[0066] Product Analysis Re...

Embodiment 2

[0067] Example 2: Preparation of (R)-[6,6'-((S,S)-2,3-butanedioloxy)]-2-bis(trifluoromethanesulfonyloxy)biphenyl

[0068] (R)-[6,6'-((S,S)-2,3-butanedioloxy)]-2,2-dihydroxybiphenyl 2.72g (10.0mmol) was dissolved in 80mL of anhydrous pyridine, Under ice cooling, 6.00 g (20.0 mmol) of trifluoromethanesulfonic anhydride was slowly added. After the dropwise addition, react under ice bath for 1 hour, slowly raise the temperature to room temperature, and continue the reaction overnight. Washed with sodium and saturated brine, the organic phase was dried with anhydrous magnesium sulfate, and the crude product was purified by column chromatography after evaporating the solvent to obtain 5.41 g of the product (R)-[6,6'-((S,S)-2 ,3-Butanedioloxy)]-2,2'-bis(trifluoromethanesulfonyloxy)biphenyl, the yield was 95%.

[0069] Product Analysis Results: 1 H NMR (300MHz, CDCl 3 ):δ1.41(d,J=6.0Hz,6H),3.86-3.96(m,2H),7.22(d,J=8.1Hz,4H),7.50(dd,J=8.1Hz,J=8.4Hz ,2H). 13 CNMR (75MHz, CDCl 3 )...

Embodiment 3

[0070] Example 3: (R)-[6,6'-((S,S)-2,3-butanedioloxy)]-2-methoxyl-2'-trifluoromethanesulfonyloxybiphenyl preparation of

[0071] Add MeOH (37mL), DMSO (55mL) and Et 3 N (3.7 mL), after mixing well, degas three times under CO atmosphere. Add (R)-[6,6'-((S,S)-2,3-butanedi Alcoholoxy)]-2,2'-bis(trifluoromethanesulfonyloxy)biphenyl (1.07g, 2.0mmol), Pd(OAc) 2 (44.9mg, 0.2mmol) and dppp (82.5mg, 0.2mmol), replace the system with CO atmosphere, and immediately use a double-ended needle to carefully transfer the degassed solution into it. Heat the oil bath to 70°C, stir and react for 2-6h, the system turns from light green to wine red. TLC tracking detection until the reaction is complete. After washing with water and extracting with ethyl acetate, the solvent was removed under reduced pressure, and the residue was washed with CH 2 Cl 2 Redissolved, silica gel column chromatography, ethyl acetate / petroleum ether as eluent, to obtain compound (R)-[6,6'-((S,S)-2,3-butanedioloxy)...

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Abstract

The invention discloses a preparation method and an application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof. The ligand and the ionic metal complex thereof have the following structural formulas. The phosphine ligand related by the invention employs biphenyl as a skeleton, and realizes completely transmission from planar chirality to axial chirality through an asymmetric desymmerization. The synthetic method is simple and economic, omits a common and complex chiral separation process in the preparation of the chiral ligand. The obtained chiral ligand has the advantages of high reactive activity, good enantiomorphous selectivity and the like in a model reaction.

Description

technical field [0001] The invention belongs to the field of chemical catalysis, and in particular, relates to a preparation method of a novel chiral phosphine-oxazoline ligand and its enantiomer or racemate and the chiral phosphine-oxazoline ligand ion Preparation method of type complex and its catalytic application. Background technique [0002] Since the study of homogeneous asymmetric catalytic reactions began in the 1960s, asymmetric catalysis has been one of the most active fields in organic synthetic chemistry, and the fastest-growing asymmetric synthesis catalyzed by chiral metal complexes is considered to be the most recent One of the most important breakthroughs in synthetic organic chemistry in the past three decades has resulted in the emergence of a large number of highly efficient chiral catalysts and new asymmetric synthesis methods. In 1972, the Rh / DIPAMP catalyst developed by Knowles et al. of Monsanto was successfully applied to the asymmetric hydrogenatio...

Claims

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Application Information

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IPC IPC(8): C07F9/6558C07F19/00B01J31/22C07B53/00C07D209/38C07D307/58C07C45/62C07C49/657
Inventor 邱立勤李庆万品
Owner SUN YAT SEN UNIV
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