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A kind of pnn ligand-metal complex catalyst and its preparation method and application

一种催化剂、铁络合物的技术，应用在有机化合物/氢化物/配位配合物催化剂、没有C-金属键的铁族有机化合物、有机化合物的制备等方向，能够解决区域选择性差等问题，达到产率高、选择性好、环境友好的效果

Active Publication Date: 2016-06-29
BIRDO (SHANGHAI) PHARMATECH CO LTD
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

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, metal 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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  • A kind of pnn ligand-metal complex catalyst and its preparation method and application
  • A kind of pnn ligand-metal complex catalyst and its preparation method and application
  • A kind of pnn ligand-metal complex catalyst and its preparation method and application

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Embodiment 1: prepare PNN ligand-iron complex

[0032] 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 diethyl ether (30mL), a red solid precipitated out, filtered and washed with diethyl ether to obtain a 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 C.

[0033] ( t Bu-P...

Embodiment 2

[0036] Embodiment 2: with embodiment 1 gained complex C to the catalytic activity experiment of the hydroboration reaction of different single alkenes

[0037]

[0038] In the glove box, add complex C (0.55 mg, 0.00125 mmol, 0.0025 equiv), THF (2 mL), 6a (84 mg, 1 mmol, 2 equiv) and HBpin (75 μL, 0.5 mmol, 1 equiv) into a 25 mL Schlenk tube and stir After homogeneity, 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 obtain colorless liquid 7a (98.6mg, 93%).

[0039] 1 HNMR (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);

[0040] 13 CNMR (CDCl 3 ,100MHz)δ83.0,42.1,27.9,24.9,22,8,21.9;

[0041] 11 BNMR (CDCl 3 ,128MHz): δ34.0.HRMS-EI(m / z): Cal...

Embodiment 3

[0116]Embodiment 3: with the catalytic activity experiment of embodiment 1 gained complex C to the hydroboration reaction of arylethene

[0117]

[0118]

[0119] In the glove box, complex C (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, after stirring evenly, add NaHBEt 3 (1M) (30μL, 0.03mmol, 0.06equiv); after stirring the reaction at room temperature for 30min, the system was exposed to air to quench; the resulting solution was concentrated at 50°C under vacuum, and then flash column chromatography (silica gel high About 5cm, pure petroleum ether as eluent) to obtain colorless liquid 9a (87.3mg, 75%).

[0120] 1 HNMR (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);

[0121] 13 CNMR (CDCl 3 ,100MHz)δ144.4,128.2,128.0,125.5,83.1,30.0,24.8;

[0122] 11 BNMR (CDCl 3 ,128MHz): δ33.7.HRMS-EI(m / z): C...

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Abstract

A PNN ligand-metal complex catalyst, a preparation method therefor and an application thereof are disclosed. The catalyst is a compound represented by the following general formula: AA or BB, wherein: M is iron or cobalt, R is a C1-C30 alkyl or a C6-C30 aryl; R1, R2, R3, R4, R5, R6, and R7 are independently selected from a hydrogen atom, a halogen atom, a C1-C30 hydrocarbyl, a C1-C30 oxygen-containing group, a C1-C30 sulfur-containing group, a C1-C30 nitrogen-containing group, a C1-C30 phosphorus-containing group, a C1-C30 silicon-containing group or other inert functional group; and X is a halogen atom or a C1-C30 alkyl. The catalyst is prepared by performing a coordination reaction of the PNN ligand and MX2 or Py2MX2. The PNN ligand-metal complex provided in the present invention allows for excellent catalysis in the hydroboration reaction of a mono-olefin.

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, its preparation method and its The application 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 methods is to...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/24C07F15/02C07F15/06C07F5/04C07F7/08C07C25/18C07C17/263C07C205/06C07C201/12C07D213/16C07D213/127C07C43/215C07C41/30C07C13/28C07C1/32
CPCC07F5/025B01J31/189B01J2231/323B01J2531/0241B01J2531/842B01J2531/845C07F15/025C07F15/065
Inventor 黄正张雷彭东杰左自青
Owner BIRDO (SHANGHAI) PHARMATECH CO LTD
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