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Resolution method of cyclic aralkyl surface chiral compound

A technology for chiral compounds and cycloalkanes, which is applied in the field of asymmetric catalytic synthesis, can solve problems such as the limited scope of substrates, and achieve the effects of high reactivity and enantioselectivity, mild reaction conditions, and easy availability of raw materials.

Active Publication Date: 2021-03-23
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the currently developed methods are limited in their substrate scope.

Method used

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  • Resolution method of cyclic aralkyl surface chiral compound
  • Resolution method of cyclic aralkyl surface chiral compound
  • Resolution method of cyclic aralkyl surface chiral compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-7

[0035] Optimization of conditions

[0036] Change the chiral phosphine nitrogen ligand, the type of organic solvent and the amount of boric acid compounds.

[0037] Put palladium trifluoroacetate (5 mol% of the amount of 1a) and chiral phosphine nitrogen ligand (5 mol% of the amount of 1a) into the reaction bottle, add 1 ml of acetone after nitrogen replacement, and stir at room temperature for 1 h. Concentrate in vacuo then, add 2 milliliters of organic solvents under nitrogen, ring aralkylimine 1a (0.1 mmol) and phenylboronic acid (150 mol% of 1a consumption in embodiment 1-6, be 100mol of 1a consumption in embodiment 7 %). React at 60°C for 15h. After removing the solvent, the pure hichiral cycloarylalkylimine 1a and the product precursor 3a were separated by direct column chromatography. Dissolve the product precursor 3a in 1ml of N,N-dimethylformamide in a reaction flask, add 6mg of sodium hydride (60% mass fraction) at 0°C, then add 26μl of allyl bromide, and stir at ...

Embodiment 8-19

[0042] Resolution of cycloarylalkylimine compounds with a series of boronic acids.

[0043] Put palladium trifluoroacetate (5 mol% of 1 dosage) and chiral phosphine nitrogen ligand L2 (5 mol% of 1 dosage) into the reaction bottle, add 1 ml of acetone after nitrogen replacement, and stir at room temperature for 1 h. Then concentrate in vacuo, add 4 milliliters of trifluoroethanol under nitrogen, ring aralkylimine 1 (0.2 mmol, ring aralkylimine used in embodiment 8-17 is rac-1a, ring aralkylimine used in embodiment 18-19 Alkylimine is rac-1b) and arylboronic acid (100mol% of 1 dosage), react at 60°C for 15h. After removing the solvent, the pure hichiral cycloarylalkylimine 1 and the product precursor 3 were separated by direct column chromatography. Dissolve the product precursor 3 with 2ml N,N-dimethylformamide in the reaction flask, add 12mg sodium hydride (60% mass fraction) at 0°C, then add 52μl allyl bromide, and stir at room temperature for 2h The product 2 was separated...

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Abstract

The invention provides a resolution method of a cyclic aralkyl surface chiral compound. A catalyst used in the resolution method is a chiral phosphine nitrogen complex of palladium. According to the method, a cyclic aralkyl imine surface chiral compound (the enantiomeric excess can reach 99.9%) and a cyclic aralkyl amine surface chiral compound (the enantiomeric excess can reach 99.4% and the diastereomer ratio can be greater than 20: 1) can be obtained, and the resolution coefficient s can reach 368. The method provided by the invention can realize catalytic resolution, and has the advantagesof simple and feasible operation, commercially available catalyst, mild conditions, low energy consumption, environment-friendliness, high resolution coefficient and high yield.

Description

technical field [0001] The invention belongs to the field of asymmetric catalytic synthesis, and relates to a method for realizing the resolution of cycloaryl alkanes hi-chiral compounds through an addition reaction catalyzed by a palladium homogeneous system. [0002] technical background [0003] Hilarchiral[2.2]cycloarane compounds are widely used in various chiral materials, and can also play an indispensable role in asymmetric synthesis as ligands or prosthetic groups. (Reference 1: (a) Morisaki, Y.; Inoshita, K.; Chujo, Y. Chem. Eur. J. 2014, 20, 8386. (b) Gibson, S. E.; Knight, J. D. Org. Biomol. Chem. 2003, 1, 1256. (c) Fringuelli, F.; Piermatti, O.; Pizzo, F.; Ruzziconi, R. Chem. Lett. 2000, 38.). At present, the methods for obtaining hichiral [2.2] cycloaryl alkanes mainly include traditional chemical resolution, chiral chromatographic separation and other methods. (Reference 2: (a) Braddock, D.C.; MacGilp, I.D.; Perry, B.G.J. Org. Chem. 2002, 67, 8679. (b) Wang, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/40C07C311/16C07C311/17C07C303/44
CPCC07B53/00C07B57/00C07C303/40C07C303/44C07C2603/92C07B2200/07C07C311/17C07C311/16
Inventor 周永贵赵洋孙蕾
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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