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Novel chiral iron complex, and preparation and use thereof

An axial chirality and reactant technology, applied in the field of new chiral iron complexes, can solve the problem of lack of chiral iron complex catalysts

Active Publication Date: 2013-04-24
瑞博(杭州)医药科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, despite a lot of attempts, so far only a few iron-catalyzed asymmetric reactions can give high enantioselectivity, the key to the problem is the lack of new and efficient chiral iron complex catalysts

Method used

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  • Novel chiral iron complex, and preparation and use thereof
  • Novel chiral iron complex, and preparation and use thereof
  • Novel chiral iron complex, and preparation and use thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Example 1: Comparison of Iron Precursors

[0056]

[0057] Weigh the iron precursor (0.015mmol), (S a , S, S)-1 (9.2mg, 0.018mmol), NaBArF (16.9mg, 0.018mmol), add 3ml of chloroform, and stir for complexation at room temperature for 4 hours. Add water (27mg, 1.5mmol) and stir for a while, then add a solution of methyl α-diazophenylacetate (52mg, 0.3mmol) and 1ml of chloroform, stir the reaction at 40°C, and monitor and track it by TLC until the reaction is complete. Column chromatography (PE / EA=5:1) gave the product as a colorless liquid. 1 HNMR (300MHz, CDCl 3 ): 7.43-7.33 (m, 5H), 5.18 (d, J=4.8Hz, 1H), 3.76 (s, 3H), 3.46 (d, J=4.8Hz, 1H).

[0058] The ee value of the product is determined by SFC, analysis conditions: Chiralcel OD-H column, sc CO 2 / i-PrOH=80:20, flow rate=2.0mL / min, detector wavelength=220nm, pressure=100bar, t R = 2.35min corresponds to (S)-isomer, t R = 2.87 min corresponds to the (R)-isomer.

[0059] The catalytic reactions of the cata...

Embodiment 2

[0062] Example 2: Ligand Comparison

[0063]

[0064] Weigh FeCl in the glove box 2 .4H 2 O (3.0mg, 0.015mmol), ligand (0.018mmol), NaBArF (16.9mg, 0.018mmol), 3ml of chloroform was added, and complexation was stirred at room temperature for 4 hours. Add water (27mg, 1.5mmol) and stir for a while, then add a solution of methyl α-diazophenylacetate (52mg, 0.3mmol) and 1ml of chloroform, stir the reaction at 40°C, and monitor and track it by TLC until the reaction is complete. Column chromatography (PE / EA=5:1) gave the product as a colorless liquid. Product NMR analysis data and ee value measuring method are with embodiment 1.

[0065] The catalytic reactions of the catalysts prepared by different ligands are shown in Table 2.

[0066] Table 2: Ligand Comparison

[0067]

[0068]

Embodiment 3

[0069] Embodiment 3: solvent comparison

[0070]

[0071] Weigh FeCl in the glove box 2 .4H 2 O (3.0mg, 0.015mmol), (S a , S, S)-1 (9.2mg, 0.018mmol), NaBArF (16.9mg, 0.018mmol), add 3ml of solvent, and stir complexation at room temperature for 4 hours. Add water (27mg, 1.5mmol) and stir for a while, then add a solution made of α-methyl diazophenylacetate (52mg, 0.3mmol) and 1ml of solvent, stir the reaction at 40°C, monitor and track by TLC until the reaction is complete, the silica gel column layer Analysis (PE / EA=5:1) gave the product as a colorless liquid. Product NMR analysis data and ee value measuring method are with embodiment 1.

[0072] The catalytic reactions of the catalysts prepared in different solvents are shown in Table 3.

[0073] Table 3: Solvent Comparison

[0074] experiment solvent Reaction time (h) Yield (%) Ee(%) 1 CHCl 3 10 90 94 2 CH 2 Cl 2 10 86 87 3 DCE 15 88 91

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Abstract

The invention relates to a novel chiral iron complex, in particular to a novel axial chiral iron complex of a nitrogen ligand. The novel chiral iron complex has the following structural formula: wherein m+n is between 2 and 3; m is an integer from 0 to 3; n is an integer from 0 to 3; X and Y are halogens, C1-C8 carboxylate radials, sulfate radicals, perchlorate radicals, 4-(3,5-bi-trifluoromethylphenyl) borate radials, 4-(pentafluoro phenyl) borate radials, 4(perfluoro tert-butoxy ) aluminum ions, 4(hexafluoro isopropoxy) aluminum ions, hexafluoro phosphate radicals, hexafluoro antimonate radials, tetrafluoro borate radials or trifluoro methanesulfonic acid radials; and X and Y are the same or different. The invention also provides a method for preparing the novel chiral iron complex. The novel axial chiral iron complex of the nitrogen ligand can catalyze the insertion reaction of dissymmetrical O-H bonds of alpha-diazotate and show high activity and enantioselectivity.

Description

technical field [0001] The invention relates to the technical field of complexes, in particular to the technical field of chiral iron complexes, in particular to a novel chiral iron complex, its preparation method and application. Background technique [0002] Asymmetric catalytic synthesis is a hotspot in the field of organic synthetic chemistry research (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). The key to asymmetric catalytic synthesis is the design and synthesis of chiral catalysts with high enantioselectivity and catalytic activity. A chiral catalyst includes two parts: a chiral ligand and a central metal, wherein the central metal determines the basic reaction performance of the catalyst. Since the first homogeneous asymmetric catalyzed cyclopropanation reaction by Nozaki et al. using Schiff base copper complexes in 1966, metal complex-catalyzed asymmetric synthesis has made great progress in the past 40 years. Peopl...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F15/02B01J31/22B01J31/26C07B53/00C07C67/31
Inventor 周其林朱守非蔡艳王立新
Owner 瑞博(杭州)医药科技有限公司
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