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Vinyl oxazolidinone compound containing quaternary carbon chiral center and preparation method thereof

A technology for vinyl oxazolidinones and compounds, applied in the fields of vinyl oxazolidinones and their preparations, compounds and their preparations, achieving the effects of high catalytic activity, mild reaction conditions, and convenient and easy-to-obtain reaction raw materials

Active Publication Date: 2013-09-25
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, asymmetric synthetic methods for the preparation of oxazolidinones containing quaternary carbon chiral centers are rarely reported.

Method used

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  • Vinyl oxazolidinone compound containing quaternary carbon chiral center and preparation method thereof
  • Vinyl oxazolidinone compound containing quaternary carbon chiral center and preparation method thereof
  • Vinyl oxazolidinone compound containing quaternary carbon chiral center and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Embodiment 1: Preparation of vinyl oxazolidinone compound Ia containing quaternary carbon chiral center

[0024] Add Pd to the reaction tube sequentially 2 (dba) 3 CHCl 3 (0.005mmol), chiral ligand 2 (Ar=Ph) (0.01mmol), compound III (R 1 =Ph) (0.2mmol), compound IV (R 2 =2-OMePh) (0.2mmol) and tetrahydrofuran (1.0mL), react at 20°C for 20 hours. After the solvent was evaporated under reduced pressure, the residue was subjected to column chromatography to obtain the product (ethyl acetate:petroleum ether=1:10-50).

[0025] Ia: R 1 = phenyl; R 2 = 2-methoxyphenyl

[0026] Yield: 95%; ee: 88%; m.p.78-80°C; [α] 25 D =+91.4(c=0.21,CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ7.43-7.46(m,2H),7.27-7.37(m,3H),7.19-7.23(m,1H),6.83-6.89(m,2H),6.71-6.75(m,1H),6.18( dd,J=10.8,17.6Hz,1H),5.49(d,J=11.2Hz,1H),5.36(d,J=17.6Hz,1H),4.69(d,J=8.8Hz,1H),4.62( d,J=8.8Hz,1H),3.74(s,3H); 13 C NMR (100MHz, CDCl 3)δ156.3, 155.9, 140.3, 136.7, 129.4, 129.0, 128.4, 128.2, 127.1, 124.0, 120....

Embodiment 2

[0027] Embodiment 2: Preparation of vinyl oxazolidinone compound Ia containing quaternary carbon chiral center

[0028] Add Pd to the reaction tube sequentially 2 (dba) 3 (0.0005mmol), chiral ligand 4 (Ar=Ph) (0.001mmol), compound III (R 1 =Ph) (1.0mmol), compound IV (R 2 =2-OMePh) (1.2mmol) and tetrahydrofuran (5.0mL), react at 40°C for 48 hours. After the solvent was evaporated under reduced pressure, the residue was subjected to column chromatography to obtain the product (ethyl acetate:petroleum ether=1:10-50).

[0029] Ia: R 1 = phenyl; R 2 = 2-methoxyphenyl

[0030] Yield: 89%; ee: 92%; m.p.78-80°C; [α] 25 D =+91.4(c=0.21,CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ7.43-7.46(m,2H),7.27-7.37(m,3H),7.19-7.23(m,1H),6.83-6.89(m,2H),6.71-6.75(m,1H),6.18( dd,J=10.8,17.6Hz,1H),5.49(d,J=11.2Hz,1H),5.36(d,J=17.6Hz,1H),4.69(d,J=8.8Hz,1H),4.62( d,J=8.8Hz,1H),3.74(s,3H); 13 C NMR (100MHz, CDCl 3 )δ156.3, 155.9, 140.3, 136.7, 129.4, 129.0, 128.4, 128.2, 127.1, 124.0, 120.2, 11...

Embodiment 3

[0031] Embodiment 3: Preparation of vinyl oxazolidinone compound IIa containing quaternary carbon chiral center

[0032] Add Pd(dba) to the reaction tube sequentially 2 (0.02μmol), chiral ligand 5 (Ar=Ph, n=1) (0.02μmol), compound III (R 1 =Ph) (0.2mmol), compound IV (R 2 =2-OMePh) (0.3mmol) and methyl tert-butyl ether (1.0mL), react at 100°C for 1 hour. After the solvent was evaporated under reduced pressure, the residue was subjected to column chromatography to obtain the product (ethyl acetate:petroleum ether=1:10-50).

[0033] IIa: R 1 = phenyl; R 2 = 2-methoxyphenyl

[0034] Yield: 92%; ee: 75%; m.p.78-80°C; [α] 25 D =+91.4(c=0.21,CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ7.43-7.46(m,2H),7.27-7.37(m,3H),7.19-7.23(m,1H),6.83-6.89(m,2H),6.71-6.75(m,1H),6.18( dd,J=10.8,17.6Hz,1H),5.49(d,J=11.2Hz,1H),5.36(d,J=17.6Hz,1H),4.69(d,J=8.8Hz,1H),4.62( d,J=8.8Hz,1H),3.74(s,3H); 13 C NMR (100MHz, CDCl 3 )δ156.3, 155.9, 140.3, 136.7, 129.4, 129.0, 128.4, 128.2, 127.1, 124.0, 12...

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Abstract

The invention provides a vinyl oxazolidinone compound containing a quaternary carbon chiral center and a preparation method thereof. According to the preparation method, vinyl glycol carbonic ester reacts with isocyanate in an organic solvent to prepare the vinyl oxazolidinone compound containing the quaternary carbon chiral center under the catalysis action of a palladium complex which is generated through the coordination of a palladium source and a chiral ligand and serves as a catalyst. The vinyl oxazolidinone compound containing the quaternary carbon chiral center, provided by the invention, has potential physiological activity and can be conveniently converted into amino alcohol containing the quaternary carbon chiral center, chirality quaternary carbon vinyl amino acid and chirality quaternary carbon serine. The preparation method provided by the invention is a high-efficiency environmentally-friendly asymmetric catalysis method and has the advantages of high catalytic activity, mild reaction conditions, convenience and easiness in availability of reaction raw materials and high enantioselectivity.

Description

technical field [0001] The invention relates to a compound in the technical field of chemical industry and a preparation method thereof, in particular to a vinyl oxazolidinone compound containing a quaternary carbon chiral center and a preparation method thereof. Background technique [0002] Chiral oxazolidinones have important physiological activities and are widely used in the field of asymmetric catalysis [(a) Zappia, G.; Gacs-Baitz, E.; Delle Monache, G.; Misiti, D. ;Nevola,L.;Botta,B.Curr.Org.Chem.2007,4,81.(b)Mukhtar,T.A.;Wright,G.D.Chem.Rev.2005,105,529.(c)Barbachyn,M.R.;Ford,C.W. Angew. Chem., Int. Ed. 2003, 42, 2010.]. Organic compounds containing quaternary carbon chiral centers exist in a large number of natural products and biologically active compounds. Asymmetric synthesis of such compounds has always been an important challenge in the field of organic synthesis. Oxazolidinone compounds containing quaternary carbon chiral centers are not only potential phys...

Claims

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Application Information

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IPC IPC(8): C07D263/24C07D263/22B01J31/24C07C215/28C07C213/00
Inventor 张勇健邢菊香赵景明阿玛尔叶江
Owner SHANGHAI JIAO TONG UNIV