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Phosphine pyridine oxazoline compound, metal complex, and preparation method and application thereof

A technology of phosphine oxazoline and metal complex, which is applied in the field of phosphine oxazoline compounds, can solve the problems of low activity and limited asymmetric hydrogenation reaction, and achieves high yield, excellent catalytic activity and high yield Effect

Active Publication Date: 2020-09-22
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Although the cobalt-catalyzed asymmetric hydrogenation of activated alkenes has made great progress, but the cobalt-catalyzed asymmetric hydrogenation of simple non-activated alkenes is relatively limited.
In 2012, Chirik's group (Monfette, S.; Turner, Z.R.; Semproni, S.P.; Chirik, P.J.J.Am.Chem.Soc.2012, 134, 4561) realized the Catalyzes the asymmetric hydrogenation of simple non-activated alkenes such as 1,1-disubstituted alkenes. This system is highly dependent on the substrate. Usually, large hindered alkenes can obtain good enantioselectivity, but the activity is also low
[0004] To sum up, in the current cobalt-catalyzed asymmetric hydrogenation of alkenes, the substrates are generally divided into activated alkenes and simple non-activated alkenes, and the latter is usually more challenging.

Method used

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  • Phosphine pyridine oxazoline compound, metal complex, and preparation method and application thereof
  • Phosphine pyridine oxazoline compound, metal complex, and preparation method and application thereof
  • Phosphine pyridine oxazoline compound, metal complex, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0141] Embodiment 1: Preparation of phosphine pyridine oxazoline compound

[0142]

[0143] Compound IIIa: Under argon protection, add 2-cyano-6-methylpyridine (1.33g, 11.2mmol), Zn(OTf) to a 100mL dry three-necked flask in sequence 2(205mg, 0.56mmol), anhydrous toluene (30mL), stirred for about 10min, then added compound VIa L-tert-leucinol (1.45g, 12.4mmol) in anhydrous toluene (10mL) solution, and the reaction system was heated Reflux for 24h, TLC tracking reaction until complete. The system was cooled to room temperature, diluted with ethyl acetate (30 mL), and then successively washed with saturated NaHCO 3 solution (3×15mL) and saturated NaCl (30mL), washed with anhydrous NaCl 2 SO 4 It was dried, filtered, concentrated, and purified by column chromatography (ethyl acetate:petroleum ether=1:5→1:3) to obtain compound IIIa (1.34 g, 55%) as a white solid.

[0144] Proton spectrum purity>97%. 1 H NMR (400MHz, CDCl 3 )δ7.93(d, J=7.8Hz, 1H), 7.63(t, J=7.7Hz, 1H), 7.23...

Embodiment 2

[0156] Embodiment 2: preparation cobalt complex

[0157]

[0158] Cobalt complex IIa:N 2 In the glove box, weigh anhydrous CoCl 2 (107mg, 0.83mmol) solid in a 50mL Schlenk bottle, add tetrahydrofuran 30mL, stir for 2h until it becomes a homogeneous blue solution, then slowly add compound Ia (300mg, 0.83mmol) to it, the color of the reaction solution gradually changes to Blue ink. After the reaction was stirred at room temperature for 10 h, the mixture was concentrated with an oil pump to obtain a solid, which was washed with an appropriate amount of ether, filtered, and dried in vacuo to obtain compound IIa (351 mg, 94%) as a blue-ink solid.

[0159] Proton spectrum purity>97%.

[0160] 1 H NMR (400MHz, CDCl 3 )δ91.83,69.13,62.45,21.43,19.61,7.17,5.75,1.56,1.54,-0.27,-13.02,-15.19,-15.63,-23.25.

[0161] IR(neat)ν max (cm -1 )=2946,2866,1654,1590,1445,1367,1181,973,932,841,754.

[0162] Elemental analysis (C 21 h 35 Cl 2 CoN 2 OP) Calculated: C, 51.23; H, 7.17;...

Embodiment 3

[0163] Example 3: Catalytic Activity Experiment of Cobalt Complex IIa on the Asymmetric Hydrogenation of α-Alkenyl Silicon

[0164]

[0165] Take the asymmetric hydrogenation process of α-diphenylsilylstyrene VIIa as an example:

[0166] N 2 In the glove box, successively weigh catalyst IIa (0.01mmol, 4.9mg), n-pentane (2mL), α-diphenylsilylstyrene VIIa (0.2mmol, 57mg) in the reaction tube, and then slowly drop Add NaBHEt 3 (20μL, 0.02mmol, 1.0M in THF), the reaction system turned dark purple, and the reaction tube was placed in an autoclave, 2bar hydrogen gas was introduced, and the reaction was carried out at room temperature for 8h. The reaction was stopped, and the reaction system was exposed to air atmosphere to quench the reaction. It was then concentrated and purified by column chromatography (pure petroleum ether as eluent) to obtain Compound VIIIa as a colorless oil.

[0167] Using the above operation, different solvents, H 2 The pressure, the consumption of c...

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Abstract

The invention discloses a phosphine pyridine oxazoline compound, a metal complex, and a preparation method and application thereof. According to the invention, the preparation methods of the phosphinepyridine oxazoline compound and the metal complex are simple, wherein the raw materials are cheap and easy to obtain, the process is environmentally friendly, reaction conditions are mild, the yieldis high, aftertreatment is simple, and large-scale production is easy. The phosphine pyridine oxazoline compound has chiral induction capability and can be complexed with metal cobalt or iron to forma chiral metal complex of the phosphine pyridine oxazoline compound. The metal complex disclosed by the invention has excellent catalytic activity in asymmetric hydrogenation reaction of alpha-alkenylsilicon, particularly in asymmetric hydrogenation reaction of alpha-silicon-based styrene compounds, and is excellent in enantioselectivity, high in yield and mild in reaction condition.

Description

technical field [0001] The invention relates to a phosphine pyridine oxazoline compound, a metal complex, a preparation method and application thereof. Background technique [0002] The asymmetric catalytic hydrogenation of olefins is one of the most widely studied reactions at present. It is an efficient, high atom-economical and environmentally friendly synthesis method for the synthesis of chiral compounds, and has been widely used in the industrial production of medicine, pesticides and fine chemicals. Widely used (Knowles, W.S.Angew.Chem.Int.Ed.2002,41,1998); (Noyori,R.Angew.Chem.Int.Ed.2002,41,2008); (Knowles,W.S.; Noyori,R. Acc. Chem. Res. 2007, 40, 1238); (Johnson, N.B.; Lennon, I.C.; Moran, P.H.; Ramsden, J.A. Acc. Chem. Res. 2007, 40, 1291); (Shultz, C.S.; Krska, S.W. Acc. Chem. Res. 2007, 40, 1320). The current development in this field is mainly based on noble metal catalytic systems, such as Ru (Ohta, T.; Ikegami, H.; Miyake, T.; Takaya, H.J. Organomet. Chem. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6558C07F15/02C07F15/06C07F7/08B01J31/24
CPCB01J31/2404B01J2231/645B01J2531/842B01J2531/845C07F7/0896C07F9/65583C07F15/025C07F15/065
Inventor 黄正左自清徐松根张雷刘桂霞
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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