Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof

A technology of iron complexes and catalysts, which is applied in the field of tridentate PNN ligand iron complex catalysts and its preparation, can solve the problems of poor regioselectivity, achieve high yield, high yield, and mild reaction conditions Effect

Inactive Publication Date: 2013-05-01
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

Another disadvantage is the poor regioselectivity during the hydroboration of arylethenes, especially when pinacolborane is used as the boron reagent
However, iron complexes containing electron-donating tridentate PNN ligands and their application as catalysts in the more common hydroboration of monoolefins have not been reported so far.

Method used

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  • Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof
  • Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof
  • Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Embodiment 1: prepare PNN ligand-iron complex A of the present invention

[0035]

[0036] In the glove box, the FeCl 2 (0.381g, 3mmol, 1equiv) and THF (50mL) were added to a 100mL Schlenk tube, and the FeCl 2 After complete dissolution, a THF solution (10 mL) of PNN ligand (1.037 mg, 3.3 mmol, 1.1 equiv) was added dropwise to the above solution, and the color gradually turned black; after stirring and reacting at room temperature for 24 h, the solvent was drained with an oil pump; The resulting solid was dissolved in CH 2 Cl 2 (10mL), then added ether (30mL), red solid precipitated, filtered and washed with ether to give brick red powder (0.953g, 72%); the above brick red powder (30mg) was dissolved in CH 2 Cl 2 (2mL) and n-hexane (2mL) in the mixed solvent that forms, then the solution is placed in the glove box, after slowly volatilizing for several days, red crystal grows, promptly obtains the PNN ligand-iron complex of the present invention Object A.

[00...

Embodiment 2

[0039] Embodiment 2: the catalytic activity experiment of complex A described in embodiment 1 to the hydroboration reaction of different single olefins

[0040]

[0041] 2a:

[0042]

[0043] In the glove box, complex A (0.55 mg, 0.00125 mmol, 0.0025 equiv), THF (2 mL), 1a (84 mg, 1 mmol, 2 equiv) and HBpin (75 μL, 0.5 mmol, 1 equiv) were added to a 25 mL Schlenk tube, After stirring well, add NaHBEt 3 (1M) (3.8 μ L, 0.00375 mmol, 0.0075 equiv); after stirring the reaction at room temperature for 10 min, the system was exposed to air to quench; the resulting solution was concentrated under vacuum, and then flash column chromatography (silica gel was about 5 cm high) , pure petroleum ether as eluent) to give colorless liquid 2a (98.6mg, 93%).

[0044] 1 H NMR (CDCl 3 ,400MHz)δ1.47-1.57(m,1H),1.39(m,2H),1.24(s,12H),1.16(m,2H),0.85(d,J=6.4Hz,6H),0.74(t ,J=7.8Hz,2H);

[0045] 13 C NMR (CDCl 3 ,100MHz)δ83.0,42.1,27.9,24.9,22,8,21.9;

[0046] 11 B NMR (CDCl 3 ,128MH...

Embodiment 3

[0136] Embodiment 3: the catalytic activity experiment of complex A described in embodiment 1 to the hydroboration reaction of arylethene

[0137]

[0138] 9a:

[0139]

[0140] In the glove box, complex A (4.4mg, 0.01mmol, 0.02equiv), toluene (2mL), acetonitrile (5μL, 10equiv), 8a (104mg, 1mmol, 2equiv) and HBpin (75μL, 0.5mmol, 1equiv ) into a 25mL Schlenk tube, and after stirring evenly, NaHBEt3(1M) (30μL, 0.03mmol, 0.06equiv) was added; after stirring and reacting at room temperature for 30min, the system was quenched by exposing the system to air; Concentration at 50°C, followed by flash column chromatography (silica gel about 5 cm high, pure petroleum ether as eluent) gave colorless liquid 9a (87.3 mg, 75%).

[0141] 1 H NMR (CDCl 3 ,400MHz)δ7.20-7.27(m,4H),7.14(t,J=7Hz,1H),2.75(t,J=8.2Hz,2H),1.21(s,12H),1.14(t,J= 8.2Hz, 2H);

[0142] 13 C NMR (CDCl 3 ,100MHz)δ144.4,128.2,128.0,125.5,83.1,30.0,24.8;

[0143] 11 B NMR (CDCl 3 ,128MHz): δ33.7.HRMS-EI(m / z): ...

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Abstract

The invention discloses a Pb(Ni1 / 3Nb2 / 3)O3 (PNN) ligand-iron complex catalyst and a preparation method and application thereof. The catalyst is a compound with a general formula shown in the specification. In the general formula, R refers to an alkane group of C1-C30 or an alkane of C6-C30, and X refers to a halogen atom. The catalyst is prepared by performing a complexing reaction between a PNN ligand and FeX2. The PNN ligand-iron complex catalyst disclosed by the invention is good in catalytic activity on a hydroboration reaction of monoolefine and not only is high in selectivity and high in yield but also is mild in reaction condition. Moreover, the preparation method for the PNN ligand-iron complex catalyst is simple, is friendly to the environment, mild in reaction condition, higher in yield, simple in postprocessing and is easy for mass production, and raw materials are low in cost and can be easily got.

Description

technical field [0001] The present invention relates to a kind of PNN ligand-iron complex catalyst and its preparation method and application, specifically, it relates to an iron complex catalyst containing an electron-donating tridentate PNN ligand and its preparation method and The application thereof in the hydroboration reaction of monoolefin belongs to the technical field of organic chemistry. Background technique [0002] Organoboronic acids and their derivatives are often used as intermediates and are widely used in organic synthesis. For example, the Suzuki-Miyaura reaction can convert organoboron compounds C(sp 3 ) is coupled with a halogenated hydrocarbon to form a C-C bond. Compared with other organometallic nucleophiles, organic boronic acid derivatives have unique stability, and many boric acid esters can be separated, purified and stored in air. Scientists have developed a variety of methods for the synthesis of organoborates. One of the commonly used method...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07F15/02C07F5/02C07F7/08
CPCC07F15/06B01J31/22C07F15/02C07F5/025B01J31/189B01J2231/323B01J2531/0241B01J2531/842B01J2531/845C07F15/025C07F15/065
Inventor 黄正张雷彭东杰
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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