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Hydroxyl-substituted pyridine oxazoline ligand and application thereof in hydrohalogenation reaction of olefin

A technology of pyridine oxazoline and ligand, which is applied in the field of hydroxyl-substituted pyridine oxazoline ligand and its application in the hydrohalogenation reaction of olefins

Active Publication Date: 2022-02-11
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

Hydroxyoxazoline ligands were reported in the literature Chem.Ber.1989,122,499 For rhodium-catalyzed asymmetric reduction of aryl ketones (22% yield, 10.4% enantioselectivity), but the reaction results are not as effective as the corresponding methyl substituted pyridine oxazoline (94% yield, 65.6% against enantioselectivity)

Method used

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  • Hydroxyl-substituted pyridine oxazoline ligand and application thereof in hydrohalogenation reaction of olefin
  • Hydroxyl-substituted pyridine oxazoline ligand and application thereof in hydrohalogenation reaction of olefin
  • Hydroxyl-substituted pyridine oxazoline ligand and application thereof in hydrohalogenation reaction of olefin

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0133] The preparation of the pyridine-oxazoline ligand that embodiment 1 hydroxyl replaces

[0134]

[0135] by As an example, the synthetic operation steps of hydroxy-substituted pyridine oxazoline are introduced:

[0136] Add substituted pyridine S1 (13.5g, 100mmol, 1.0equiv.) and dichloromethane (150mL) into a 500mL reaction flask, add m-chloroperoxybenzoic acid (32.5g, 150mmol, 1.5equiv.) in batches under stirring, Reaction at room temperature, monitored by TLC. After the reaction, add K 2 CO 3 (27.6g, 200mmol, 2.0equiv.), stirred at room temperature for 30min, then filtered under reduced pressure, and the filtrate was spin-dried to obtain pyridine nitrogen oxide compound S2, which was directly put into the next reaction.

[0137] Add S2, dichloromethane (150mL), trimethylsilyl cyanide (14.4g, 150mmol, 1.5equiv.) into a 100ml egg-shaped flask, stir at room temperature for 15 minutes, then add N,N-dimethylcarbamoyl chloride (15.6 g, 150mmol, 1.5equiv.), stirred ov...

Embodiment 2

[0159] The hydrochlorination reaction of embodiment 2 palladium catalysis olefin

[0160]

[0161] Pd(CH 3 EN) 2 Cl 2 (6.5mg, 0.025mmol, 5mol%), L1 (9.2mg, 0.0375mmol, 7.5mol%), and NCS (133.3mg, 1.0mmol, 2.0equiv.) were weighed into the sealed tube in turn and pumped to keep the system in Under nitrogen atmosphere, then sequentially add the dry mixed solvent CH 3 CN:CH 2 Cl 2 (2:8, 5.0mL), alkene substrate (0.5mmol, 1.0equiv), water (10.0μL), triethylamine (25μL, 1M in DCM, 0.025mmol, 5mol%) and triisopropylsilane ( 0.3mL, 1.5mmol, 3.0equiv), stirred at room temperature until complete. After the reaction finishes, pass through a silica gel short column (300-400 mesh, CH 2 Cl 2 Elution), the solvent was spin-dried, and the product was obtained by column chromatography (300-400 mesh, PE:EA elution).

[0162]

[0163] Colorless liquid (111.7mg, 89% yield). 1 H NMR (400MHz, CDCl 3 )δ7.82–7.80(m,2H),7.71–7.68(m,2H),3.67(t,J=7.6Hz,2H),3.50(t,J=6.8Hz,2H),1.83–1.76(m...

Embodiment 3

[0270] The hydrobromination reaction of embodiment 3 palladium catalysis olefin

[0271]

[0272] Pd(hfacac) 2 (26.0mg, 0.05mmol, 10mol%), L3 (17.5mg, 0.075mmol, 15mol%), LiClO 4 (53.4mg, 0.5mmol, 1.0equiv) or HCl (50μL, 40mol%, 4.0M in dioxane), Na-NMBI (229.0mg, 1.0mmol, 2.0equiv) were weighed into the sealed tube in sequence and pumped to keep the system in Under nitrogen atmosphere, then sequentially add the dry mixed solvent CH 3 CN:CH 2 Cl 2 (4:6, 5.0mL), alkene substrate (0.5mmol, 1.0equiv), H 2 O (4.0 μL for HCl, 10 μL for LiClO 4 ) and triisopropylsilylhydrogen (0.22mL, 1.1mmol, 2.2equiv), stirred and reacted at room temperature. After 6 hours, Na-NMBI (114.5 mg, 0.5 mmol, 1.0 equiv) and triisopropylsilylhydrogen (0.11 mL, 0.55 mmol, 1.1 equiv) were added to continue the reaction until complete. After the reaction finishes, pass through a silica gel short column (300-400 mesh, CH 2 Cl 2 Elution), the solvent was spin-dried, and the product was obtained by ...

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Abstract

The invention discloses a hydroxyl-substituted pyridine oxazoline ligand and an application thereof in an anti-Markov hydrohalogenation reaction of olefin. Specifically, the invention discloses a hydroxyl-substituted pyridine oxazoline ligand as shown in a formula I which is described in the specification. The ligand can realize anti-Markov hydrochlorination and hydrobromination reactions of olefin, including terminal olefin and internal olefin, and also can be mixed olefin to singly obtain primary alkyl halide. Besides, the reaction conditions are mild, the regioselectivity is high, and the substrate universality is wide.

Description

technical field [0001] The present invention relates to hydroxyl-substituted pyridine oxazoline ligands and their use in the hydrohalogenation of olefins. Background technique [0002] Alkyl halides are widely used synthetic building blocks in organic synthesis, and this fragment also widely exists in natural products, drug molecules, pesticides and material molecules. Traditional methods of synthesizing such compounds usually undergo functional group transformation, especially from the hydrohalogenation of alcohols. The hydrohalogenation of olefins is an important reaction in organic chemistry, and it is the most direct and efficient method to synthesize alkyl halides from cheap and easily available olefins as raw materials. The reaction often uses acid as a catalyst and follows the Markov addition rule to obtain branched chain-based alkyl halides. However, Martens' hydrohalogenation reaction to obtain primary alkyl chlorides is extremely challenging. In the patent US201...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D413/04B01J31/22C07D209/48C07C19/01C07C17/08C07C17/087C07C29/62C07C31/36C07C45/63C07C49/16C07C47/14C07C201/12C07C205/37C07D311/18C07C67/307C07C69/63C07C253/30C07C255/10C07C303/40C07C311/53C07D333/68C07D307/42C07D333/16C07C67/287C07C69/78C07C255/54C07C69/747C07D493/14
CPCC07D413/04B01J31/2217C07D209/48C07C17/08C07C29/62C07C45/63C07C201/12C07D311/18C07C67/307C07C253/30C07C303/40C07D211/18C07D333/68C07D307/42C07D333/16C07C67/287C07D493/14B01J2531/824C07C2601/02C07C19/01C07C17/087C07C31/36C07C49/16C07C47/14C07C205/37C07C69/63C07C255/10C07C311/53C07C69/78C07C255/54C07C69/747
Inventor 刘国生李响金剑波陈品红
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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