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A chiral nitrogen nitrogen phosphine tridentate ligand based on a ferrocene skeleton and an application thereof

A ferrocene and skeleton technology, applied in the field of chiral phosphine nitrogen tridentate ligands, can solve the problems of high price and long synthesis route of spiro ring ligands, and achieve easy purification, high industrial application value, water and air stable effect

Active Publication Date: 2018-11-09
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis route of such spirocyclic ligands is long and expensive

Method used

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  • A chiral nitrogen nitrogen phosphine tridentate ligand based on a ferrocene skeleton and an application thereof
  • A chiral nitrogen nitrogen phosphine tridentate ligand based on a ferrocene skeleton and an application thereof
  • A chiral nitrogen nitrogen phosphine tridentate ligand based on a ferrocene skeleton and an application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1: Synthesis of Ligand LI2

[0021]

[0022] Dissolve (S)-Ugi-amine 1 (5.14g, 20mmol) in 50mL ether, under nitrogen protection and ice-salt bath cooling, add n-butyllithium (16mL, 2.5mol / L) dropwise to the reaction system, dropwise After completion, the temperature was slowly raised to room temperature, and the reaction was stirred for 3 hours. Diphenylphosphine chloride (8.82 g, 40 mmol) was added dropwise under cooling in an ice-salt bath, and after the drop was completed, the temperature was slowly raised to room temperature, and the reaction was stirred for 12 hours. The reaction was quenched with saturated sodium bicarbonate solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain compound 2 (5.38 g, 61%).

[0023]

[0024] Compound 2 (4.41 g, 10 mmol) was dissolved in 8.0 mL of acetic anhydride, and reacted at 55° C. for 4 hours. After the reaction was completed, excess acetic ...

Embodiment 2

[0029] Example 2: Synthesis of Ligand LI3

[0030] The preparation method of crude product 3 is the same as that of Example 1.

[0031]

[0032] Crude products 3 (0.46 g, 0.1 mmol) and 5 (0.53 g, 0.2 mmol) were added to the reaction flask, and after replacing the nitrogen, 5 mL of methanol was added and reacted at 50° C. for 15 hours. Concentration and column chromatography gave yellow ligand LI3 (0.40 g, 51%).

[0033]

[0034] 1 H NMR (600MHz, CDCl 3 )δ7.48(m, 2H), 7.35(m, 3H), 7.15(s, 2H), 7.08(t, J=7.1Hz, 3H), 6.96(t, J=6.8Hz, 2H), 5.96( s,1H),4.50(s,1H),4.27(s,1H),4.08(m,1H),4.05(d,J=7.0Hz,1H),4.04(s,5H),4.03(d,J =6.8Hz,1H 1H),3.64(s,1H),3.02–2.92(m,1H),2.22–1.92(m,4H),1.49(t,J=10.2Hz,2H),1.39(d,J =5.4Hz, 3H), 1.28(dd, J=6.8, 5.3Hz, 6H), 1.23(d, J=6.8Hz, 6H), 1.17(d, J=6.8Hz, 6H), 1.09–0.96(m ,2H),0.14(s,1H),-0.20(d,J=11.5Hz,1H). 13 C NMR (151MHz, CDCl 3 )δ152.07,150.28,139.96,139.88,136.45,136.38,135.13,134.96,133.54,132.71,132.56,129.16,128.31,128.26,128.1...

Embodiment 3

[0035] Example 3: Synthesis of Ligand LI5

[0036]

[0037] (S)-Ugi-amine 1 (2.57g, 10mmol) was dissolved in 25mL of diethyl ether, under the condition of nitrogen protection and ice-salt bath cooling, n-butyllithium (8mL, 2.5mol / L) was added dropwise to the reaction system, and the dropwise After that, it was slowly raised to room temperature, and the reaction was stirred for 3 hours. Bis(3,5-di-tert-butylphenyl)phosphorous chloride (8.90 g, 20 mmol) was added dropwise under cooling in an ice-salt bath. After the drop was completed, the temperature was slowly raised to room temperature, and the reaction was stirred for 24 hours. The reaction was quenched with saturated sodium bicarbonate solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain product 7 (3.79g, 57%).

[0038]

[0039] Compound 7 (3.33 g, 5 mmol) was dissolved in 4.0 mL of acetic anhydride and reacted at 55° C. for 4 hours. After t...

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Abstract

The invention belongs to the technical field of asymmetric catalysis and specifically relates to a chiral nitrogen nitrogen phosphine tridentate ligand based on a ferrocene skeleton and an applicationthereof. A coordination compound is obtained by the disclosed chiral nitrogen nitrogen phosphine tridentate ligand base on the ferrocene skeleton complexed with a transition metal precursor, the complex is used as a precious metal catalyst, and is successfully applied to high efficiency asymmetric hydrogenation of aromatic ketone. Compared with other tridentate ligands, the ligand is simple to synthetize, is stable to water and air, and easy to prepare on a large scale, shows high activity and high enantioselectivity on carbon and oxygen double bond, and has greater implementation value and social and economic benefits.

Description

technical field [0001] The invention belongs to the technical field of asymmetric catalysis, and in particular relates to a chiral tridentate ligand based on a ferrocene skeleton and an application thereof. Background technique [0002] Chirality is one of the essential attributes of nature, and the use of chiral drugs and chiral pesticides can often achieve better therapeutic or insecticidal effects. Asymmetric catalytic hydrogenation, as one of the important methods to obtain chiral compounds, has the advantages of good atom economy and high stereoselectivity, and has always been one of the research hotspots. [0003] The combination of metal and chiral ligand has become the mainstream of asymmetric catalytic hydrogenation due to its excellent catalytic performance. As early as the 1970s, William S. Knowles used metal rhodium and organophosphine ligands to realize asymmetric catalytic hydrogenation for the first time, and applied it to the industrial synthesis of chiral d...

Claims

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Application Information

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IPC IPC(8): C07F17/02B01J31/24C07B53/00C07C29/145C07C33/22C07C33/20C07C33/46C07C33/18C07D317/54
CPCB01J31/2404B01J2231/643B01J2531/827C07B53/00C07B2200/07C07C29/145C07D317/54C07F17/02C07C33/22C07C33/20C07C33/46C07C33/18
Inventor 钟为慧凌飞年三飞
Owner ZHEJIANG UNIV OF TECH
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