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A kind of phosphoramidite ligand and its preparation method and application

A phosphoramidite, the phosphoramidite technology, applied in the direction of organic chemistry methods, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as lack

Active Publication Date: 2018-04-10
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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  • A kind of phosphoramidite ligand and its preparation method and application
  • A kind of phosphoramidite ligand and its preparation method and application
  • A kind of phosphoramidite ligand and its preparation method and application

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 HNMR (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,J...

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Abstract

The invention relates to the field of chemical catalysis, and discloses a kind of phosphoramidite ligand, its preparation method and application. The synthesized phosphoramidite ligands and their enantiomers or their racemates use biphenyl as the backbone, and undergo a central chiral asymmetric induction reaction to achieve complete central chirality to axial chirality transfer. The synthesis method of the phosphoramidite ligand and its enantiomer or its raceme is simple and economical, and the common and complicated chiral resolution process is avoided when preparing the chiral ligand. The present invention uses phosphoramidite ligands and their enantiomers or their racemates to form complexes with active metal iridium to catalyze the asymmetric addition reaction of N-protected isatin and arylboronic acid, and obtains a good catalytic effect. The product can be obtained in a yield of more than 96% and an 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 the metabolites of plants such as Baphicacanthuscusia (Nees) Bremek, Isatisindigotica For.t, and microbial metabolites; The 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 an...

Claims

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Application Information

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