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Derivative containing halogen light active oxazolidinone and preparation method thereof

A kind of compound, the technology of basic conditions, applied in the field of halogen-containing photoactive oxazolinone derivatives and its preparation

Inactive Publication Date: 2013-05-01
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 derivative containing halogen light active oxazolidinone and a preparation method thereof. The structural formula of the compound is shown as the formula I. N-Bromosuccinimide serves as a bromine source, a complex of chiral phosphine ligand and lewis acid serves as a catalyst, olefin substrates with different catalyzing structures are subjected to asymmetric bromine amine cyclization reaction, and the derivative containing halogen light active oxazolidinone is synthesized and prepared through a simple column chromatography post-processing step. An ee (enantiomer excess) value can achieve highest to 97%. The reaction can be amplified to a gram level, the ee value of products after recrystallization can achieve 99%, and a potential industrial application value is provided. Reaction products can be further derived into various useful compounds, and product application values are achieved.

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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IPC IPC(8): C07D263/26C07D203/24C07D303/36C07D301/02
CPCC07D203/24C07D303/36C07D301/02C07D263/26
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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