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A kind of β-hydroxy phosphate and its asymmetric synthesis method

A technology of hydroxy phosphate and carbonyl phosphate, which is applied in the field of chiral β-hydroxy phosphate and its asymmetric synthesis, can solve the problems that the asymmetric transfer hydrogenation synthesis of chiral β-hydroxy phosphate has not been reported, and achieve the reaction Mild conditions, convenient experimental operation, simple synthesis effect

Active Publication Date: 2020-06-30
CHINA THREE GORGES UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But so far, there is no report on the asymmetric transfer hydrogenation synthesis of chiral β-hydroxyphosphate

Method used

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  • A kind of β-hydroxy phosphate and its asymmetric synthesis method
  • A kind of β-hydroxy phosphate and its asymmetric synthesis method
  • A kind of β-hydroxy phosphate and its asymmetric synthesis method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Example 1: Asymmetric Synthesis of (S)-2-Hydroxy-2-Phenylethyl Diphenylphosphonate

[0030]

[0031] 0.2mmol of 2-oxo-2-phenylethyl diphenylphosphonate was added to the test tube, followed by the addition of HCOONa (2eq, 27mg), 0.002mmol of catalyst A, CF 3 CH 2 OH / H 2 O(50 / 1)1mL, replace nitrogen, react at 40°C for 4h. After the reaction was finished, it was washed with water, extracted 3 times with ethyl acetate, and the combined organic phases were concentrated to dryness. The isolated yield: 61% (dichloromethane: methanol = 20:1), and the product (S)-2-hydroxyl- The asymmetric synthesis of 2-phenylethyldiphenylphosphonate had an ee value of 90.5%. HPLC separation conditions: chiral column Daicel OD-H column, mobile phase: n-hexane / isopropanol=90:10 (volume ratio), flow rate: 1.0 ml / min, wavelength: 260 nm, column temperature: 30 degrees Celsius, t1=15.18 minutes, t2=20.72 minutes; 1 H NMR (400MHz, CDCl 3 ): δ=7.88-7.80(m, 4H), 7.61-7.56(m, 2H), 7.53-7.47(m,...

Embodiment 2

[0032] Example 2: Asymmetric Synthesis of (S)-2-Hydroxy-2-Phenylethyl Diphenylphosphonate

[0033]

[0034] 0.2mmol of 2-oxo-2-phenylethyl diphenylphosphonate was added to the test tube, followed by adding HCOONa (2eq, 27mg), 0.002mmol catalyst B, CF 3 CH 2 OH / H 2 O(50 / 1)1mL, replace nitrogen, react at 40°C for 4h. After the reaction was finished, it was washed with water, extracted 3 times with ethyl acetate, the combined organic phases were concentrated to dryness, the isolated yield: 64% (dichloromethane: methanol = 20:1), and the product (S)-2-hydroxyl- The asymmetric synthesis of 2-phenylethyldiphenylphosphonate had an ee value of 96%.

Embodiment 3

[0035] Example 3: Asymmetric Synthesis of (S)-2-Hydroxy-2-Phenylethyl Diphenylphosphonate

[0036]

[0037] 0.2mmol of 2-oxo-2-phenylethyl diphenylphosphonate was added to the test tube, followed by adding HCOONa (2eq, 27mg), 0.002mmol catalyst C, CF 3 CH 2 OH / H 2 O(50 / 1)1mL, replace nitrogen, react at 40°C for 4h. After the reaction was finished, it was washed with water, extracted 3 times with ethyl acetate, the combined organic phase was concentrated to dryness, the isolated yield: 67% (dichloromethane: methanol = 20:1), and the product (S)-2-hydroxyl- The asymmetric synthesis of 2-phenylethyldiphenylphosphonate had an ee value of 92%.

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Abstract

The invention relates to beta-hydroxy phosphate and an asymmetric synthesis method thereof. A beta-hydroxy phosphate compound with high enantioselectivity is obtained by using beta-carbonyl phosphateas a raw material, using trifluoroethanol and water as solvents, using sodium formate as a hydrogen source and using a complex of single-sulfonyl chiral diamine and metals of ruthenium, rhodium and iridium through asymmetry transfer hydrogenation; the reaction condition is mild; the asymmetric synthesis method is simple and convenient to operate; raw materials are easy to obtain, the application range of a substrate is wide, and enantioselectivity is high. The used chiral diamine ligand, compared to a chiral phosphine ligand, is stable, simple to synthesize and relatively low in price, and iswidely applied to the asymmetry transfer hydrogenation reaction.

Description

technical field [0001] The invention belongs to the technical field of asymmetric catalysis, and in particular relates to a chiral β-hydroxy phosphate and an asymmetric synthesis method thereof. Background technique [0002] Chiral diamine ligands are more stable than chiral phosphine ligands, easy to synthesize, and relatively cheap, and are widely welcomed in asymmetric transfer hydrogenation reactions. But so far, there is no report on the asymmetric transfer hydrogenation synthesis of chiral β-hydroxyphosphate. Contents of the invention [0003] The object of the present invention is to provide a kind of optically active β-hydroxy phosphate and preparation method thereof, described compound is: [0004] [0005] where Ar is selected from any of the. [0006] The R 1 for hydrogen, C 1 -C 10 Any one of alkyl, alkoxy, haloalkyl, halogen, phenyl; [0007] R 2 for hydrogen and C 1 -C 10 alkyl; [0008] In the definition of compound II given above, the terms u...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/32A61P9/12A61P31/12A01P1/00A01P3/00A01P13/00A01P21/00C07B53/00
CPCA61P9/12A61P31/12C07B53/00C07B2200/07C07F9/3229C07F9/3288
Inventor 周海峰张凯莉陈淡宜刘祈星陈永盛
Owner CHINA THREE GORGES UNIV