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A chiral azasemicrown ether multidentate ligand and its preparation method and application

A technology of chiral aza and multidentate ligands, applied in chemical instruments and methods, catalytic reactions, organic compounds/hydrides/coordination complex catalysts, etc., to achieve mild reaction conditions and simple preparation methods

Active Publication Date: 2021-10-12
ZHENGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The chiral azasemicrown ether multidentate ligand prepared by the present invention contains both an aza five-membered ring amino alcohol skeleton and an aza four-membered ring amino alcohol skeleton, which has not been reported yet

Method used

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  • A chiral azasemicrown ether multidentate ligand and its preparation method and application
  • A chiral azasemicrown ether multidentate ligand and its preparation method and application
  • A chiral azasemicrown ether multidentate ligand and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] A chiral azasemicrown ether multidentate ligand, , Ar 1 = Ar 2 = Ph.

[0033] Its preparation method is:

[0034] (1) Take a 100 mL round bottom flask and add compound Ⅱ (Ar 1 = Ph) (0.9 g, 3.54 mmol, 1.0 equiv), anhydrous potassium carbonate (1.47 g, 10.62 mmol), added to 14 mL N,N -Dimethylformamide, then slowly added compound I (0.718 g, 3.72 mmol) to the solution, reacted at room temperature for 16 h, then added 50 mL of phosphate buffer solution to the reaction system to terminate the reaction, extracted 3×50 mL with EtOAc, combined organic phase, washed with saturated brine, washed with anhydrous Na 2 SO 4 Drying, rotary evaporation to remove the solvent, the crude product was purified by column chromatography, and the developing solvent was ethyl acetate / petroleum ether=1 / 9 to obtain compound III (Ar 1 = Ph) 1.12 g, yield 79%;

[0035] (2) Take a 100 mL round-bottomed flask and weigh compound Ⅲ (Ar 1 = Ph) (0.63 g, 1.57 mmol), add 8 mL of ethanol ...

Embodiment 2

[0037] The difference between this example and Example 1 is that compound IV is replaced by (Ar 2 = 4-CH 3 -C 6 h 4 ), ligand L (Ar 1 =Ph, Ar 2 = 4-CH 3 -C 6 h 4 ) with a yield of 92%, melting point: 76.4-77.1 ℃; [α] D = +50.5 ( c = 0.82,CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ ppm 7.67 (d, J = 7.6 Hz, 2H), 7.55 (d, J =7.5 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7.31-7.24 (m, 7H), 7.18-7.00 (m, 7H),6.60 (s, 1H), 6.52 (s, 1H), 4.32 (t, J = 8.0 Hz, 1H), 3.98-3.94 (m, 1H), 3.28(s, 2H), 3.21-3.12 (m, 3H), 2.87-2.81 (m, 2H), 2.44-2.37 (m, 1H), 2.29-2.21(m, 8H), 2.13 (s, 3H), 1.99-1.93 (m, 1H), 1.80-1.72 (m, 1H), 1.65-1.56 (m,1H), 1.54-1.42 (m, 1H ); 13 C{ 1 H) NMR (100 MHz; CDCl 3 ) Δ ppm 152.6, 147.2, 146.6,143.0, 141.4, 136.6, 136.3, 129.2, 129.0, 128.6, 128.2, 127.4, 126.26.4, 125.8, 124.7, 78.6, 72.9, 58.6, 58.6, 58.6, 58.6, 58.6, 58.6. , 56.8, 55.1, 50.1, 29.7, 24.0, 21.1, 20.99, 20.4, 19.5. HRMS calcd for C 44 h 49 N 2 o 3 [M+H] + :653.3738. Found: ...

Embodiment 3

[0039] The difference between this example and Example 1 is that compound IV is replaced by (Ar 2 = 4-CF 3 -C 6 h 4 ), ligand L (Ar 1 =Ph, Ar 2 = 4-CF 3 -C 6 h 4 ) yield 94%, melting point: 77.3-77.9 ℃; [α] D = +39.5 ( c = 0.68, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ ppm 7.71 (d, J = 8.2 Hz, 2H), 7.64 (d, J =7.4 Hz, 2H), 7.57-7.49 (m, 10H), 7.33-7.27 (m, 4H), 7.19 (t, J = 7.4 Hz, 1H), 6.51 (s, 2H), 4.44 (t, J = 7.8 Hz, 1H), 3.97-3.94 (m, 1H), 3.41 (d, J = 13Hz, 1H), 3.31-3.18 (m, 4H), 3.01-2.95 (m, 1H), 2.84-2.79 (m, 1H), 2.38-2.31(m, 1H), 2.10 (s, 3H), 2.07 -2.06 (m, 1H), 2.03-1.93 (m, 2H), 1.87-1.79 (m, 1H), 1.71-1.62 (m, 1H), 1.60-1.51 (m, 1H); 13 C{ 1 H) NMR (100 MHz; CDCl 3 ) Δ ppm152.6, 150.1, 147.7, 146.3, 146.1, 129.0, 128.6, 128.4, 127.4, 126.9,126.7, 126.1, 125.9, 125.4, 125.2, 123.4,79.4, 122.4,79.4 75.9, 71.9, 71.7, 59.4, 56.2, 55.2, 50.0, 29.5, 24.1, 20.4, 19.4. HRMScalcd for C 44 h 43 f 6 N 2 o 3 [M+H] + : 761.3172. Found: 761....

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Abstract

A kind of chiral azasemicrown ether polydentate ligand, its general structural formula is: , wherein Ar 1 、Ar 2 C respectively 6 h 5 , 4‑CF 3 -C 6 h 4 , 4‑CH 3 -C 6 h 4 One of. At the same time, the invention also discloses its preparation method. A group of chiral azasemicrown ether polydentate ligands with novel structures provided by the present invention provide more choices for the screening and optimization of catalysts for related catalytic asymmetric reactions. At the same time, the preparation method is simple and the reaction conditions are mild. Through nucleophilic substitution and A series of chiral azasemicrown ether polydentate ligands can be prepared by two steps of reductive amination.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a chiral azasemicrown ether polydentate ligand and a preparation method and application thereof. Background technique [0002] In the field of asymmetric catalysis, metal complex catalysts based on different ligands and different metal combinations have been continuously developed and applied. Among them, the semi-crown ether polydentate ligands containing the aza five-membered ring amino alcohol skeleton and the semi-crown ether polydentate ligand containing the aza four-membered ring amino alcohol skeleton have achieved excellent results in many catalytic asymmetric reactions. structures, and they also have good applications in the synthesis of natural products. The difference between the aminoalcohol structure of these two ligands is only a methylene group. However, through the comparison of experimental results, it is found that the performance...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D403/10C07D487/20B01J31/22
CPCB01J31/2217B01J2231/4205B01J2231/64C07D403/10C07D487/20
Inventor 华远照杨小超王瑞丽刘萌萌耿宇欢郭亚军王敏灿
Owner ZHENGZHOU UNIV