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Chiral metal rhodium complex as well as synthesis method and application thereof in synthesis of chiral 1,5-dicarbonyl compound

A technology for dicarbonyl compounds and rhodium complexes, applied in the field of chiral metal rhodium complexes, can solve the problems of complicated operation steps, difficult to effectively separate diastereomers and the like

Inactive Publication Date: 2019-07-23
FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, metal rhodium complex catalysts are mainly synthesized by a chiral auxiliary ligand strategy, that is, firstly, a pair of diastereomers are obtained through a coordination reaction between a rhodium dimer and a chiral auxiliary group, and then separated by a column, and finally desorbed. Removal of chiral prosthetic ligands yields a series of optically pure rhodium-centered chiral complexes [see Meggers, E. Chem. Eur. J. 2010, 16, 752-758. or Gong, L.; Wenzel, M.; Meggers , E.Acc.Chem.Res.2013,46,2635-2644.], this type of method has problems such as cumbersome operation steps and difficult effective separation of diastereomers

Method used

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  • Chiral metal rhodium complex as well as synthesis method and application thereof in synthesis of chiral 1,5-dicarbonyl compound
  • Chiral metal rhodium complex as well as synthesis method and application thereof in synthesis of chiral 1,5-dicarbonyl compound
  • Chiral metal rhodium complex as well as synthesis method and application thereof in synthesis of chiral 1,5-dicarbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0115] Embodiment 1: chiral metal rhodium complex sample 1 # preparation of

[0116] Prepare chiral rhodium complex, comprising the following steps:

[0117] 1) First Response

[0118] At room temperature, add chiral pinene pyridine ligand (L) (1.02g, 4.10mmol), RhCl 3 Hydrate (360.1 mg, 1.37 mmol), 2-ethoxyethanol / water (3:1, 68 mL). Stir at 125° C. for 40 hours under the protection of argon and avoid light. After the solvent was removed under reduced pressure, the residue was separated by column chromatography to obtain the product Rh-Cl.

[0119]

[0120] R f =0.30 (ethyl acetate / petroleum ether=1 / 10, v / v); orange-red solid, yield 25%.

[0121] The product detection results are as follows:

[0122] 1 H NMR (400MHz, CDCl 3 ): δ=7.66(d, J=8.0Hz, 1H), 7.61(d, J=8.0Hz, 1H), 7.57(dd, J=1.4Hz, 7.8Hz, 1H), 6.94-6.90(m, 1H ),6.70-6.66(m,1H),5.99(d,J=8.0Hz,1H),3.87(t,J=5.5Hz,1H),3.11(dd,J=2.1Hz,17.1Hz,1H), 3.00(dd,J=3.0Hz,17.1Hz,1H),2.58-2.52(m,1H),2.31-2.27(m,1H),1.35...

Embodiment 2

[0136] Embodiment 2: chiral metal rhodium complex sample 2 # and 3 # preparation of

[0137] Chiral metal rhodium complex sample 2 # ~3 # The differences between the preparation method and Example 1 are listed in Table 1.

[0138] Table 1

[0139] Sample serial number first reaction reaction conditions Second Reaction Reaction Conditions The ratio of 2-ethoxyethanol to water 2 #

Embodiment 3

[0140] Embodiment 3: chiral metal rhodium complex sample 4 # and 5 # preparation of

[0141] Chiral metal rhodium complex sample 4 # and 5 # Sample 1 in preparation method and embodiment 1 # The same, the difference is that the RhCl 3 Hydrates were replaced by the same molar number of RhBr 3 Hydrate and RhI 3 Hydrate, the obtained samples are respectively recorded as sample 4 # and sample 5 # .

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Abstract

The invention discloses a chiral metal rhodium complex as well as a synthesis method and an application thereof in synthesis of a chiral 1,5-dicarbonyl compound. The synthesis method of the chiral metal rhodium complex comprises steps as follows: a) RhX3 and L-chiral pinene pyridine are subjected to a first reaction, and chiral Rh-X is obtained; b) chiral Rh-X and an alkyl nitrile compound are subjected to a second reaction, and the chiral metal rhodium complex is prepared. The method is simple and easy to operate and can be used for catalyzing multiple types of alpha, beta-unsaturated acyl imidazole and silyl enol ether compounds.

Description

technical field [0001] The invention relates to a chiral metal rhodium complex, a synthesis method thereof, and an application thereof in synthesizing chiral 1,5-dicarbonyl compounds, belonging to the technical field of organic synthesis. Background technique [0002] In recent years, metal-centered chiral complexes have shown good application prospects in asymmetric catalytic reactions due to their high catalytic activity and good stereoselectivity. It has developed rapidly in the past three years. [0003] At present, metal rhodium complex catalysts are mainly synthesized by a chiral auxiliary ligand strategy, that is, a pair of diastereomers is obtained through a coordination reaction between a rhodium dimer and a chiral auxiliary group, and then separated by a column, and finally desorbed. Removal of chiral prosthetic ligands yields a series of optically pure rhodium-centered chiral complexes [see Meggers, E. Chem. Eur. J. 2010, 16, 752-758. or Gong, L.; Wenzel, M.; Meg...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07B53/00C07D233/64C07D409/06C07D405/06C07C67/18C07C69/738
CPCB01J31/184B01J2231/4205B01J2531/822C07B53/00C07B2200/07C07C67/18C07D233/64C07D405/06C07D409/06C07F15/0073C07C69/738
Inventor 康强龚军
Owner FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI