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Phosphoramidite ligand as well as preparation method and application thereof

A phosphoramidite and ligand technology, applied in the field of phosphoramidite ligands and their preparation, can solve problems such as lack

Active Publication Date: 2015-05-13
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, until now, there is a lack of methods to systematically regulate the dihedral angle of such ligands.

Method used

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  • Phosphoramidite ligand as well as preparation method and application thereof
  • Phosphoramidite ligand as well as preparation method and application thereof
  • Phosphoramidite ligand as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0060] Example 1 The prepared (R)-[6,6'-((S)-1,2-propylene glycol oxygen)]-2,2'-N,N-diisopropylphosphoramidite (16) is example

[0061]

[0062] Synthesis of (R)-1,2-propanediol dimesylate (2)

[0063] (R)-1,2-propanediol (1g, 13.14mmol), CH 2 Cl 2 (50mL), Et 3 N (3.66mL, 26.28mmol) system, slowly add methanesulfonyl chloride (2.03mL, 23.28mmol) dropwise in CH at 0°C 2 Cl 2 (20mL) solution, dripping over 1h, the reaction continued to stir for 1h, slowly rose to room temperature and stirred for 20h. The reaction solution was poured into 100 mL of 1N HCl solution, CH 2 Cl 2 Extraction, anhydrous Na 2 SO 4 dry. The solvent was spin-dried under reduced pressure, and the crude product was recrystallized to obtain 3.97 g of a white solid product with a yield of 67%. 1 H NMR (400MHz, CDCl 3 )δ5.14-5.09(m,1H),4.23-3.92(m,2H),3.25(s,6H),1.39(m,3H)ppm.

[0064] Synthesis of (R)-[6,6'-((S)-1,2-propanedioloxy)]-2,2'-dihydroxybiphenyl

[0065] 2,2',6,6'-Tetrahydroxybipheny...

Embodiment 2

[0072] Example 2 to prepare (R)-[6,6'-((S,S)-2,3-butanedioloxy)]-2,2'-N,N-bis[(1S)-1- Phenylethyl]phosphoramidite (17) as an example

[0073]

[0074] Synthesis of (R)-[6,6'-((S,S)-2,3-butanedioloxy)]-2,2'-dihydroxybiphenyl

[0075] 2,2',6,6'-Tetrahydroxybiphenyl (1.77g, 8.12mmol), anhydrous cesium carbonate (6.08g, 18.67mmol), anhydrous DMF (232mL), heating and stirring at 80°C, slowly drop into A solution of (R,R)-2,3-butanediol dimesylate (1.98g, 8.12mmol) in anhydrous DMF (81mL) was added dropwise over 4 hours. The reaction mixture was continued at 80 °C for 12 h. DMF was removed under reduced pressure, extracted with ethyl acetate, anhydrous Na 2 SO 4 dry. The solvent was spin-dried under reduced pressure, and the crude product was subjected to silica gel column chromatography to obtain a light yellow solid. Product yield: 1.28 g, yield: 58%. product 1 H NMR (300MHz, CDCl 3 )δ7.26-7.19(m,2H),6.78-6.71(m,4H),6.11(s,2H),3.95-3.85(m,2H),1.37(d,J=5.4Hz,6H)ppm.

...

Embodiment 3

[0078] Example 3 to prepare (S)-[6,6'-((R,R)-2,4-pentanedioloxy)]-2,2'-N,N-bis[(1R)-1- Phenylethyl]phosphoramidite (18) as an example

[0079]

[0080] Synthesis of (S)-[6,6'-((R,R)-2,4-pentanedioloxy)]-2,2'-dihydroxybiphenyl

[0081] 2,2',6,6'-Tetrahydroxybiphenyl (0.80g, 3.67mmol), anhydrous cesium carbonate (3.56g, 10.93mmol), anhydrous DMF (120mL), stirred at room temperature. A solution of (2S,4S)-pentanediol p-toluenesulfonate (1 g, 2.43 mmol) in anhydrous DMF (40 mL) was added dropwise, and the solution was completed after 4 hours. Continue to react at room temperature for 120h. DMF was removed under reduced pressure, extracted with ethyl acetate, anhydrous Na 2 SO 4 dry. The solvent was spin-dried under reduced pressure, and the crude product was subjected to silica gel column chromatography to obtain 0.69 g of a light yellow solid product with a yield of 68%. 1 H NMR (400MHz, CDCl 3 )δ7.20-7.14(m,2H),6.72(d,J=8.1Hz,2H),6.65-6.58(m,2H),4.69-4.57(m,2H),1.36(d,...

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Abstract

The invention relates to the field of chemical catalysis and discloses a phosphoramidite ligand as well as a preparation method and an application thereof. The synthesized phosphoramidite ligand and an enantiomer or a racemate of the phosphoramidite ligand take biphenyl as a framework and are subjected to an asymmetric induced reaction of axial chirality to realize complete transfer from central chirality to axial chirality. A synthetic method for the phosphoramidite ligand and the enantiomer or the racemate of the phosphoramidite ligand is simple and economic, and a common and complex chiral resolution process is avoided during chiral ligand preparation. The phosphoramidite ligand and the enantiomer or the racemate of the phosphoramidite ligand is employed to form the ligand together with active metal-iridium for catalyzing an asymmetric addition reaction of N-protected isatin and arylboronic acid, a very good catalytic effect is achieved, and a product can obtain the yield of more than 96% and the enantiomeric excess (ee) value of more than 92%.

Description

technical field [0001] The invention belongs to the field of chemical catalysis, and relates to a class of phosphoramidite ligands and a preparation method and application thereof. Background technique [0002] Isatin, also known as indoloquinone, is an important natural product widely distributed in animals, plants and human body. Isatin is found in plants such as Baphicacanthuscusia (Nees) Bremek, Isatis indigotica For.t and other metabolites of microorganisms; ) symbiotic marine bacteria (Alterornonassp.) can also produce isatin, which has a strong inhibitory effect on pathogenic fungi (ogaridium callinectes) [Curr Microbiol., 2004, 48, 441]. Asymmetric addition of isatins to arylboronic acids can prepare isatins with chiral carbons substituted at the 3-position, which are core structural fragments of many natural alkaloids and bioactive molecules. The catalysts currently used in this type of reaction are composed of active metals rhodium, palladium, ruthenium and chira...

Claims

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Application Information

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IPC IPC(8): C07F9/6574B01J31/22C07D209/38C07B53/00
Inventor 邱立勤庄玥
Owner SUN YAT SEN UNIV
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