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NCP ligand, metal iridium complex thereof, and preparation method and application of complex

A compound and an independent technology, applied in the field of NCP ligands, can solve problems such as lack, and achieve good regioselectivity, good enantioselectivity, and mild reaction conditions

Active Publication Date: 2021-12-31
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Asymmetric transfer hydrogenation has been widely studied because of its advantages of not using dangerous hydrogen, not using expensive hydrogenation equipment, and being simple to operate (Gladiali, S.; Alberico, E. Chem. Soc. Rev. 2006, 35, 226-236; C. Zheng; S.-L. You. Chem. Soc. Rev. 2012, 41, 2498-2518; Wang, D.; Astruc, D. Chem. Rev. 2015, 115, 6621-6686.), but turn Metal-catalyzed asymmetric transfer hydrogenation of 1,1-diarylethenes lacks any reports so far

Method used

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  • NCP ligand, metal iridium complex thereof, and preparation method and application of complex
  • NCP ligand, metal iridium complex thereof, and preparation method and application of complex
  • NCP ligand, metal iridium complex thereof, and preparation method and application of complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～4

[0154] Examples 1-4: Preparation of Ligands 1A-1D

[0155] Preparation of Ligand 1A: (S)- tBu NC O P tBu

[0156] step 1:

[0157]

[0158] Add 3-cyanophenol (1.9 g, 10 mmol), ZnCl 2 (2.7g, 20mmol), anhydrous chlorobenzene (60mL), L-tert-leucinol (2.1g, 18mmol), and the reaction system was heated to reflux for 24h. The system was cooled to room temperature, ethyl acetate (20 mL) and water (30 mL) were added to dissolve the solids in the system, filtered, the filtrate was separated, and the organic phase was washed with saturated NaHCO 3 solution (3×10mL) and saturated NaCl (20mL), washed with anhydrous NaCl 2 SO 4 It was dried, concentrated by filtration, and purified by column chromatography (ethyl acetate:petroleum ether=1:4) to obtain a white solid 4a (1.01 g, 46%), with a purity of >97% by HS.

[0159] 1 H NMR (400MHz, CDCl 3 )δ9.07(s,1H),7.54(s,1H),7.36(d,J=7.7Hz,1H),7.19(t,J=7.9Hz,1H),6.92(d,J=8.1Hz, 1H), 4.35(dt, J=15.6, 9.2Hz, 2H), 4.08(dd, J=10.0, 6.9Hz,...

Embodiment 5～8

[0186] Embodiment 5~8: preparation complex 2A~2D

[0187] Preparation of complex 2A:

[0188]

[0189] In an argon glove box, ligand 1A (0.5mmol, 181.5mg) and [Ir(COD)Cl] 2 (0.24mmol, 161.0mg) was added to a Schleck sealed tube equipped with a stirring bar, and then 10mL of toluene solvent was added, the sealed tube was sealed, and the glove box was taken out. The reaction was reacted in the bath for 12 hours, then the reaction system was cooled to room temperature, the solvent was sucked dry under high vacuum, the residue was washed with n-pentane (3×30 mL) and filtered through a fritted funnel equipped with diatomaceous earth, the filtrate was collected, and then The solvent was pumped dry under high vacuum condition to obtain the red complex 2A (162.5 mg, 55%), with a purity of >97% in H spectrum.

[0190] 1 H NMR (400MHz,C 6 D. 6 )δ7.21(d, J=7.5Hz, 1H), 6.80(d, J=7.7Hz, 1H), 6.72(t, J=7.7Hz, 1H), 4.29(dd, J=9.4, 3.5Hz, 1H), 4.20(dd, J=9.1, 3.5Hz, 1H), 3.63(t, J=9....

Embodiment 9

[0203] Example 9: Catalytic activity experiment of complex 2A on the asymmetric transfer hydrogenation reaction of 1,1-diaryl substituted ethylene

[0204] Take the transfer hydrogenation process of 1-(2-methyl)phenyl-1-phenylethene 8a as an example:

[0205]

[0206] First in the argon gas glove box, the complex 2A (0.004mmol), NaO t Bu (0.006mmol), EtOH (5.43mmol, 0.25mL), 1-(2-methyl)phenyl-1-phenylethene 8a (48.5mg, 0.25mmol) were added to a 10mL sealed tube. After the reaction was stirred at room temperature for 36 h, it was quenched by exposure to air. Then the solvent was removed by rotary evaporation, and flash column chromatography (a mixture of petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate=40:1) gave colorless liquid 9a.

[0207]

[0208] (S)-1-Methyl-2-(1-phenylethyl)benzene (9a). Colorless liquid (48.0mg, 98%), purity>97% by H-spectrum. 1 H NMR (400MHz, CDCl 3 )δ7.18(m,4H),4.31(q,J=7.1Hz,0H),2.22(s,1H),1.60(d,J=7.2Hz,1H). 13...

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Abstract

The invention discloses an NCP ligand, a metal iridium complex thereof, and a preparation method and application of the complex. The NCP ligand has a structure as shown in a formula 1, and can be complexed with metal iridium to form the chiral metal iridium complex of the NCP ligand as shown in a formula 2, and the complex has excellent catalytic activity in hydrogenation reaction of diaryl substituted olefin, and has the advantages of better regioselectivity, better enantioselectivity, high yield, mild reaction conditions and the like especially in asymmetric transfer hydrogenation reaction.

Description

technical field [0001] The invention relates to NCP ligand, its metal iridium complex, preparation method and application. Background technique [0002] 1,1-Substituted aryl alkanes are important backbones of many bioactive molecules, including drug molecules like tolterodine and sertraline. 1,1-Diarylethanes have been extensively studied by scientists for their potential therapeutic effects on inflammation, insomnia, cancer, and obesity. Transmetal-catalyzed asymmetric hydrogenation of 1,1-diarylethenes is the most direct and effective method to construct 1,1-diarylethanes. Although significant progress has been made in the transmetal-catalyzed asymmetric hydrogenation of 1,1-diarylethenes, few reports have been reported on the asymmetric hydrogenation of 1,1-diarylethenes with sterically hindered orientation in the ortho position. [0003] The Diegiez group reported the asymmetric hydrogenation of such substrates catalyzed by chiral metal iridium (Mazuela, J.; Verendel, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00C07F9/653C07D263/14C07D263/10B01J31/22C07D307/38C07D333/12C07B53/00C07C5/03C07C15/12C07C15/24C07C17/354C07C25/18C07C41/20C07C43/164C07C43/172C07C67/303C07C69/76C07C209/70C07C211/48
CPCC07F15/0033C07F9/653C07D263/14C07D263/10B01J31/188B01J31/1875C07B53/00C07C5/03C07C17/354C07C41/20C07C67/303C07C209/70C07D307/38C07D333/12B01J2231/645B01J2531/827C07B2200/07C07C15/12C07C25/18C07C43/164C07C69/76C07C15/24C07C211/48C07C43/1742
Inventor 黄正钱露刘桂霞
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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