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Ortho-bicyclic amine compound and its preparation method and chiral product

A technology for cyclic amines and compounds, applied in the field of asymmetric synthesis, can solve the problems of cumbersome operation and narrow substrate application range.

Active Publication Date: 2020-03-10
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] To sum up, in recent years, the asymmetric synthesis of this kind of o-bicyclic amine compounds has made some progress, but it still has great limitations. The products obtained by hydrogenation method are mainly meso, and the substrate is suitable The scope is also very narrow; while multi-step synthesis can prepare o-bicyclic amine compounds, but the operation is cumbersome and requires chiral resolution

Method used

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  • Ortho-bicyclic amine compound and its preparation method and chiral product
  • Ortho-bicyclic amine compound and its preparation method and chiral product
  • Ortho-bicyclic amine compound and its preparation method and chiral product

Examples

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preparation example Construction

[0030] The present invention provides a method for preparing an o-bicyclic amine compound, the o-bicyclic amine compound is a compound of the structure shown in formula (4), the method comprising: in the presence of a chiral catalyst, the formula ( 1) The compound of the shown structure is subjected to an addition reaction with hydrogen, wherein the chiral catalyst is a complex of the structure shown in formula (2);

[0031] Formula (4)

[0032] Formula 1)

[0033] Wherein, X' is selected from CH or N; R 1 , R 2 , R 3 and R 4 each independently hydrogen, halogen, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted arylbenzyl, wherein, for substituted alkyl, substituted cycloalkyl, substituted aryl and substituted arylbenzyl The substituents are each independently selected from one or more of fluorine, chlorine, bromine, nitro, methyl, methoxy, trifluorome...

preparation example 1

[0149] (1) Dissolve (R,R)-1,2-diphenyl-ethylenediamine (20mmol, purchased from Bailingwei Technology Co., Ltd. 24694 brand) in dichloromethane (30mL), and dissolve in P-methylphenylsulfonyl chloride (20mmol, purchased from Bailingwei Technology Co., Ltd. 283322 brand) in dichloroethane (30mL) was added dropwise (dropped within 30min), continued to react at 0°C for 1h, and then reduced pressure Rotary evaporation, the solid was separated and purified by column chromatography (the eluent was dichloromethane / methanol with a volume ratio of 10:1), so as to obtain 15 mmol of the formula (R, R)-(3-1-1-1) The chiral diamine shown has a yield of 75%, and the identification data of this chiral diamine is: 1 H NMR (300MHz, CDCl 3 ): δ7.31(d, J=8.3Hz, 2H), 7.18-7.09(m, 10H), 6.97(d, J=8.3Hz, 2H), 4.37(d, J=5.2Hz, 1H), 4.12 (d,J=5.2Hz,1H),2.32(s,3H),1.49(br,3H); 13 C NMR (75MHz, CDCl 3 ): δ142.5, 139.2, 137.2, 129.1, 128.4, 128.2, 127.5, 127.4, 127.0, 126.9, 126.6, 63.2, 60.5, 21.4. ...

preparation example 2

[0153] (1) According to the method of step (1) in Preparation Example 1, the difference is that methanesulfonyl chloride (20mmol, purchased from Alfa Aisha Chemical Co., Ltd. A13383 brand) is used instead of p-methylphenylsulfonyl chloride, and Reaction at 0°C for 1 h, thereby obtaining 14.6 mmol of chiral diamine represented by the formula (R,R)-(3-1-1-2), with a yield of 73%. The identification data of the chiral diamine for: 1 H NMR (300MHz, CDCl 3 ): δ7.34-7.26(m, 10H), 4.56(d, J=5.1Hz, 2H), 4.21(d, J=5.1Hz, 2H), 2.26(s, 3H); 13 C NMR (75MHz, CDCl 3 ): δ141.9, 139.7, 128.7, 128.6, 127.9, 127.8, 126.9, 126.7, 63.4, 60.2, 40.7.

[0154] (2) According to the method of step (2) in Preparation Example 1, the difference is that the chiral diamine used is the chiral diamine shown in the above formula (R, R)-(3-1-1-2) (145 mg, 0.5 mmol), recrystallized to obtain 275 mg of a red solid (ie, the complex shown in formula (R, R)-4j);

[0155] (3) According to the method of step (3...

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Abstract

The invention relates to the field of asymmetric synthesis methods, and discloses a preparation method of o-bicyclic amine compounds. The method comprises the step of enabling a compound having a structure as shown in a formula (1) and hydrogen to be subjected to an addition reaction in presence of a chiral catalyst, wherein the chiral catalyst is a complex having a structure as shown in a formula (2). The invention also provides chiral products of the o-bicyclic amine compounds prepared by the method, and the o-bicyclic amine compounds. After the method is adopted, the selective hydrogenation reduction of the compound having the structure as shown in the formula (1) is realized by using the hydrogen, so that octahydrogenated products, i.e., the o-bicyclic amine compounds shown in a formula (4) are produced with low cost. The formula (1), the formula (2) and the formula (4) are described in the description.

Description

technical field [0001] The invention relates to the field of asymmetric synthesis methods, in particular to an ortho-bicyclic amine compound, a preparation method thereof and a chiral product. Background technique [0002] Chiral ortho-diamine compounds are an important class of compounds that constitute structural units in drugs and bioactive molecules (for example: penicillin, cephalosporin and antiviral drug oseltamivir, shown in the following formula). In addition, chiral ortho-diamine compounds are an important class of "dominant ligands", which can be applied in asymmetric catalytic reactions. Therefore, it is of great significance to synthesize chiral ortho-diamine compounds with high enantioselectivity. [0003] [0004] Although there are many reports on the asymmetric synthesis of chiral ortho-diamines, most of them focus on acyclic chiral ortho-diamines, and there are still great challenges in the asymmetric synthesis of cyclic chiral ortho-diamines. . For e...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/18C07D215/20C07D215/06C07D241/38
CPCC07B2200/07C07D215/06C07D215/18C07D215/20C07D241/38
Inventor 范青华张建伟马文鹏陈飞何艳梅
Owner INST OF CHEM CHINESE ACAD OF SCI
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