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Derivative containing halogen light active oxazolidinone and preparation method thereof

A technology of substrates and compounds, applied in organic chemistry and other fields

Inactive Publication Date: 2014-08-13
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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  • Derivative containing halogen light active oxazolidinone and preparation method thereof
  • Derivative containing halogen light active oxazolidinone and preparation method thereof
  • Derivative containing halogen light active oxazolidinone and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Embodiment 1, synthetic compound formula I-a (see structural formula I-a)

[0079]

[0080] Ts in the above formula represents p-toluenesulfonyl.

[0081] Weigh into the reaction test tube ligand (shown in formula III-a) (0.00691g, 0.01mmol) and Sc (OTf) 3 (0.00492g, 0.01mmol), a mixed solvent of PhMe / DCM=3 / 1 (v / v, 4.0mL) was added, and stirred at 0°C for 0.5h. Add NBS (0.1068g, 0.60mmol), stir at 0°C for 5min and cool to -50°C, then add the olefin substrate (shown in formula II-a) (0.1415g, 0.5mmol) in PhMe / DCM=3 / 1 (v / v, 1.0 mL) solution, reacted at -50°C for 48h. After the reaction, add triethylamine (0.5mL) to quench the reaction, directly spin dry and perform column chromatography (eluent is petroleum ether: ethyl acetate=5 / 1, v / v) to obtain 0.1589g white solid oxazole The phenone product (shown by formula I-a) has a yield of 88% and an enantiomeric excess of 96% (as determined by HPLC).

[0082] HPLC conditions: chiral AD-H column, mobile phase: mixed solven...

Embodiment 2

[0085] Embodiment 2, synthetic compound formula I-a (see structural formula I-a) by ligand formula III-b

[0086]

[0087] Ts in the above formula represents p-toluenesulfonyl.

[0088] Weigh the ligand (shown in formula III-b) (0.00788g, 0.01mmol) and Sc(OTf) in the reaction test tube 3 (0.00492g, 0.01mmol), a mixed solvent of PhMe / DCM=3 / 1 (v / v, 4.0mL) was added, and stirred at 25°C for 0.5h. Add NBS (0.1068g, 0.60mmol), stir at 25°C for 5min and cool to -50°C, then add the olefin substrate (shown in formula II-a) (0.1415g, 0.5mmol) in PhMe / DCM=3 / 1 (v / v, 1.0 mL) solution, reacted at -50°C for 48h. After the reaction, add triethylamine (0.5mL) to quench the reaction, directly spin dry and perform column chromatography (eluent is petroleum ether: ethyl acetate=5 / 1, v / v) to obtain 0.1532g white solid oxazole The phenone product (shown by formula I-a) has a yield of 85% and an enantiomeric excess of 97% (as determined by HPLC).

[0089] HPLC conditions: chiral AD-H column,...

Embodiment 3

[0091] Embodiment 3, synthetic compound formula I-b (see structural formula I-b)

[0092]

[0093] Ts in the above formula represents p-toluenesulfonyl.

[0094] Weigh into the reaction test tube ligand (shown in formula III-a) (0.00691g, 0.01mmol) and Sc (OTf) 3(0.00492g, 0.01mmol), a mixed solvent of PhMe / DCM=3 / 1 (v / v, 4.0mL) was added, and stirred at 0°C for 0.5h. Add NBS (0.1068g, 0.60mmol), stir at 0°C for 5min and cool to -50°C, then add the olefin substrate (shown by formula II-b) (0.1345g, 0.5mmol) in PhMe / DCM=3 / 1 (v / v, 1.0 mL) solution, reacted at -50°C for 72h. After the reaction, add triethylamine (0.5mL) to quench the reaction, directly spin dry and perform column chromatography (eluent is petroleum ether: ethyl acetate=5 / 1, v / v) to obtain 0.1381g white solid oxazole The phenone product (shown by formula I-b) has a yield of 79% and an enantiomeric excess of 96% (as determined by HPLC).

[0095] HPLC conditions: chiral AD-H column, mobile phase: mixed solvent...

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Abstract

The invention discloses a halogen-containing optically active oxazolidinone derivative and a preparation method therefor. The structural formula of the compound is shown as formula I. In the present invention, N-bromosuccinimide is used as a bromine source, and a complex of a chiral phosphine ligand and a Lewis acid is used as a catalyst to catalyze olefin substrates with different structures in an asymmetric bromine amine cyclization reaction; the optically active oxazolidinone derivative is synthetically prepared through a simple post-processing step of column chromatography. An enantiomer excess value (ee value) can reach up to 97%. The reaction can be scaled up to gram level and the ee value of the product after recrystallization can reach 99%, therefore the reaction has a potential industrial application value. Furthermore, the reaction product can be further derived into various useful compounds so as to achieve the application values of the product.

Description

technical field [0001] The invention relates to a halogen-containing photoactive oxazolinone derivative and a preparation method thereof. Background technique [0002] The halogenation reaction of alkenes is one of the most important elementary reactions in synthetic chemistry, which provides a very simple and effective way for the functionalization of alkenes. The asymmetric halogenation reaction of alkenes can introduce two chiral heteroatoms on the double bond at the same time, and the halogen atoms in the product can undergo various transformations, such as stereoselective substitution reactions, etc., thus becoming an important in organic synthesis. synthon. Due to its great importance, the asymmetric halogenation of alkenes has aroused widespread interest among chemists, and great progress has been made in recent years. At present, there are many reports on chiral amine-catalyzed systems, but most of them are limited to asymmetric halide lactonization. There are als...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D263/26C07D203/24C07D303/36C07D301/02
CPCC07D303/36C07D301/02C07D263/26C07D203/24
Inventor 史一安黄德顺刘晓芹李利君刘伟刚
Owner INST OF CHEM CHINESE ACAD OF SCI
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