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Chiral phosphite ligand derived from tartaric acid and its preparation method and use

A phosphite ligand, tartaric acid technology, applied in the preparation of organic compounds, the preparation of carbon-based compounds, chemical instruments and methods, etc., can solve the problems of product racemization, reducing enantioselectivity, etc.

Inactive Publication Date: 2016-03-02
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In the asymmetric 1,4-conjugated addition reaction, excellent chiral ligands have shown specificity to the reaction substrate; moreover, under the reaction conditions of different temperatures, the enantioselectivity of the reaction is different, The results show that there are different catalytically active species in the reaction system, and some ligand copper complex active species are easy to cause product racemization, which reduces the enantioselectivity of the reaction; therefore, the development of new chiral phosphorus ligands, and It is still very necessary to explore its application in asymmetric catalytic synthesis methods

Method used

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  • Chiral phosphite ligand derived from tartaric acid and its preparation method and use
  • Chiral phosphite ligand derived from tartaric acid and its preparation method and use

Examples

Experimental program
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Embodiment 1~2

[0023] Examples 1-2: Preparation of chiral phosphite ligands derived from tartaric acid.

Embodiment 3~17

[0024] Examples 3-17: Preparation of ligand / Cu catalyst and its application in the asymmetric 1,4-addition reaction of diethylzinc to cycloenone.

Embodiment 1

[0025] Example 1: Preparation of chiral phosphite ligand L1.

[0026] .

[0027] Under nitrogen atmosphere, add (3R,4R)-1-benzyl-3,4-dihydroxypyridine-2,5-dione X (132.7mg, 0.6 mmol), (R)-phosphorous oxychloride Y (463mg, 1.32mmol) and 4-dimethylaminopyridine (14.6mg, 0.12mmol), add 10mL tetrahydrofuran as a solvent, stir to completely dissolve the solid, and cool the solution to -15 0.34 mL of triethylamine was slowly added dropwise and kept at -15 °C for 0.5 h, and then placed at room temperature for 1 h. The solvent was removed under reduced pressure, 20 mL of toluene was added and stirred thoroughly, the solid was filtered off, the filtrate was concentrated, and separated by flash chromatography to obtain 234 mg of ligand L with a yield of 46%.

[0028] White foamy solid, 46% yield. Melting point: 157-158°C; [α] D 20 =-297.2(c=0.11,CH 2 Cl 2 ); 31 PNMR (161MHz, CDCl 3 ):δ142.80; 1 HNMR (400MHz, CDCl 3 ):δ4.65-4.74(dd, J =24,16Hz,2H),5.33-5.37(m,1H),5.41-5.43(...

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Abstract

The invention relates to two tartaric acid-derived chiral phosphite ligands as well as a synthetic method and application thereof in asymmetric 1,4-conjugated addition reaction of diethylzinc cyclic ketene. The chiral ligands are white solids, and can stably exist in a nitrogen atmosphere; the used raw material is low in price and easily available; the synthetic method is simple. The ligands react with a Cu salt in an organic solvent in the nitrogen atmosphere, ligands / Cu catalyst are prepared in an in-situ manner, and the asymmetric 1,4-conjugated addition reaction is catalyzed, so as to obtain a beta-ethyl cyclic ketone product with optical activity. The percent conversion and the enantioselectivity are respectively up to 99% and 91%.

Description

technical field [0001] The invention relates to a chiral phosphite ligand derived from tartaric acid, a preparation method and application thereof. It is applied to prepare ligand / Cu complex catalyst, catalyze the asymmetric 1,4-conjugate addition reaction of diethyl zinc to cyclic enone, and synthesize optically active b-ethyl cyclic ketone. Background technique [0002] The 1,4-conjugated addition of organometallic reagents to α,β-unsaturated carbonyl compounds is one of the important reactions for the formation of C-C bonds. Asymmetric conjugated addition products can be applied to the preparation of natural products, and biologically active Drugs or intermediates, such as erogorgiaene, (-)-pumiliotoxinC, β-D-mannosylphosphomycoketide, etc. Chiral ligands play a key role in achieving highly asymmetric chiral-induced 1,4-conjugated addition reactions. Currently reported successful ligands are: phosphoramidite ligands, phosphite ligands, P, O and P, N ligands, etc. [Perez...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6574B01J31/22C07C45/69C07C49/403C07C49/395
Inventor 王来来邢爱萍
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI