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Method for asymmetric functionalization of nickel-hydrogen catalytic olefin migration promoted by ligand relay strategy

A nickel-hydrogen catalyzed olefin and functionalization technology, applied in organic chemistry methods, chemical instruments and methods, compounds of elements of Group 4/14 of the periodic table, etc., can solve problems such as unreported asymmetric hydrogen functionalization, and achieve The effect of reducing difficulty and mild reaction conditions

Active Publication Date: 2021-06-11
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, at present, the asymmetric hydrogen functionalization of alkenes is limited to the in-situ hydrogen functionalization of alkenes (as shown in the following reaction formula), and there is no report on the remote asymmetric hydrogen functionalization of alkenes

Method used

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  • Method for asymmetric functionalization of nickel-hydrogen catalytic olefin migration promoted by ligand relay strategy
  • Method for asymmetric functionalization of nickel-hydrogen catalytic olefin migration promoted by ligand relay strategy
  • Method for asymmetric functionalization of nickel-hydrogen catalytic olefin migration promoted by ligand relay strategy

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044]

[0045]In a glove box filled with nitrogen, nickel chloride ethylene glycol dimethyl ether complex (2.2mg, 5.0mol%), chiral ligand L26* (7.2mg, 6.0mol%), potassium fluoride (23.2mg ,2.0equiv), achiral ligand L21 [0.21mg, 0.1mL (2.1mg / mL toluene solution)] dissolved in toluene (0.60mL) and DMPU (0.20mL), stirred for 10 minutes and then added the above olefin (30μL , 0.20mmol), 4-iodoanisole (94.0mg, 0.40mmol) and DMMS (49.3μL, 0.40mmol), the reaction tube was sealed and taken out from the glove box, and reacted at 0°C for 24 hours. After the reaction was completed, the reaction solvent was removed by concentration under reduced pressure, and column chromatography separation and purification obtained the target product (colorless oil, yield 75%). 1 H NMR (500MHz, CDCl 3 )δ7.34–7.29(m,2H),7.29–7.25(m,2H),7.20(d,J=8.8Hz,3H),6.87(d,J=8.7Hz,2H),3.91(t,J =7.8Hz, 1H), 3.81(s, 3H), 2.04(q, J=7.8Hz, 2H), 1.37–1.28(m, 2H), 0.97(t, J=7.4Hz, 3H); 13 C NMR (126MHz, CDCl 3 )δ1...

Embodiment 2

[0047]

[0048] In a glove box filled with nitrogen, nickel chloride ethylene glycol dimethyl ether complex (2.2mg, 5.0mol%), chiral ligand L26* (7.2mg, 6.0mol%), potassium fluoride (23.2mg ,2.0equiv), achiral ligand L21 [0.42mg, 0.2mL (2.1mg / mL toluene solution)] dissolved in toluene (0.60mL) and DMPU (0.20mL), stirred for 10 minutes and then added the above olefin (26μL , 0.20mmol), 4-iodoanisole (94.0mg, 0.40mmol) and DMMS (49.3μL, 0.40mmol), the reaction tube was sealed and taken out from the glove box, and reacted at room temperature for 24 hours. After the reaction was completed, the reaction solvent was removed by concentration under reduced pressure, and column chromatography separation and purification obtained the target product (colorless oil, yield 73%). 1 H NMR (500MHz, CDCl 3 )δ7.18–7.12(m,2H),7.08–7.02(m,3H),6.90–6.84(m,3H),4.10(t,J=6.7Hz,1H),3.82(s,3H),2.98 –2.84(m,2H),2.21–2.13(m,1H),1.95–1.84(m,2H),1.82–1.74(m,1H); 13 C NMR (126MHz, CDCl 3 )δ157.8, 139...

Embodiment 3

[0050]

[0051] In a glove box filled with nitrogen, nickel chloride ethylene glycol dimethyl ether complex (2.2mg, 5.0mol%), chiral ligand L26* (7.2mg, 6.0mol%), potassium fluoride (23.2mg ,2.0equiv), achiral L21 [0.42mg, 0.2mL (2.1mg / mL toluene solution)] was dissolved in toluene (0.60mL) and DMPU (0.20mL), stirred for 10 minutes and then added the above olefin (32.2mg, 0.20mmol), 4-iodoanisole (94.0mg, 0.40mmol) and DMMS (49.3μL, 0.40mmol), the reaction tube was sealed and taken out from the glove box, and reacted at room temperature for 24 hours. After the reaction was completed, the reaction solvent was removed by concentration under reduced pressure, and column chromatography separation and purification obtained the target product (white solid, yield 81%). 1 H NMR (500MHz, CDCl 3 )δ7.78(d, J=6.9Hz, 2H), 7.49(t, J=7.4Hz, 1H), 7.42(t, J=7.5Hz, 2H), 7.30(d, J=8.6Hz, 2H) ,6.90(d,J=8.6Hz,2H),6.44(d,J=8.2Hz,1H),5.06(q,J=7.6Hz,1H),3.81(s,3H),2.03–1.85(m, 2H), 0.96(t, J=7....

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Abstract

The invention discloses a method for asymmetric functionalization of nickel-hydrogen catalytic olefin migration promoted by a ligand relay strategy. Under the action of a metal nickel salt, an achiral ligand, a chiral ligand, alkali, a hydrogen source, an additive and the like, olefin and various electrophilic reagents are dissolved in an organic solvent for reaction, and the chiral compound with excellent regioselectivity and enantioselectivity is obtained. According to the method, the chiral compound containing various functional groups can be efficiently synthesized, the product has high enantioselectivity, the raw materials are simple and easy to obtain, and operation is easy and convenient.

Description

technical field [0001] The method of the invention belongs to the fields of organic chemistry and medicinal chemistry, and relates to the preparation of optically active 1,1-diaryl, benzylamine, benzyl ether, and benzyl borate by migrating asymmetric functional groups of olefins and various coupling reagents , allyl benzene, allyl amine, propargyl benzene, propargyl amine, dialkyl carboxylic acid and derivatives thereof, dialkyl alcohol or ether, dialkyl phosphate and other structural compounds. Background technique [0002] optionally in an inert sp 3 The introduction of functional groups at the C–H bond position can greatly simplify the synthetic route, allowing simpler and more readily available raw materials to be used for retrosynthesis analysis. However, the current development strategy still has certain limitations. In order to distinguish multiple very similar sp 3 C–H bond to improve selectivity. Most strategies require the introduction of polar directing groups...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C43/205C07C41/30C07C233/73C07C231/12C07D213/61C07F5/02C07F7/18C07C233/07C07F9/40C07C69/16C07C67/29
CPCC07C41/30C07C231/12C07D213/61C07F5/025C07F7/1804C07F7/1892C07F9/4056C07F9/4075C07C67/29C07B2200/07C07C2602/10C07C43/205C07C233/73C07C233/07C07C69/16Y02P20/584
Inventor 朱少林张遥何玉立
Owner NANJING UNIV
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