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Amino acid derived chiral acyclic secondary amine-tertiary amine catalyst and its preparation method and application

A tertiary amine catalyst and cyclic secondary amine technology are applied in the field of novel chiral acyclic secondary amine-tertiary amine catalysts and their preparation, and can solve the problems of catalytic efficiency, stereoselectivity control or unsatisfactory substrate application range, etc. Excellent enantioselectivity control ability, efficient catalytic performance, good effect of stereocatalytic selectivity

Active Publication Date: 2020-09-29
YUNNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] It can be seen that although chiral primary amines and cyclic chiral secondary amine catalysts have achieved important results, in some asymmetric catalytic conversion processes, their catalytic efficiency, stereoselectivity control or substrate application range are still limited. Ideal

Method used

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  • Amino acid derived chiral acyclic secondary amine-tertiary amine catalyst and its preparation method and application
  • Amino acid derived chiral acyclic secondary amine-tertiary amine catalyst and its preparation method and application
  • Amino acid derived chiral acyclic secondary amine-tertiary amine catalyst and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] The first specific preparation process of the chiral acyclic secondary amine-tertiary amine catalyst derived from amino acid comprises the following steps:

[0053] Step (1): In a 100mL round-bottomed flask, dissolve N-Boc-protected (S)-tert-leucine (a-1, 2.31g, 10mmol) in 20mL of dry dichloromethane solvent, and then dissolve the It was cooled to 0°C; then, 20 mL of a dry dichloromethane solution of DCC (2.16 g, 10.5 mmol) was slowly added dropwise to the above solution system within 1 h (1 h); during the dropping process, a white solid was observed in the system , after the dropwise addition, the reaction system continued to stir for 30min; within 1h, slowly added 20mL of a dry dichloromethane solution of diethylamine (0.73g, 10mmol) dropwise; after the dropwise addition, the reaction body was transferred The reaction was continued at room temperature for 12 h until the reaction of the raw materials was completed as monitored by TCL. The reaction solution was suction...

Embodiment 2

[0063] The difference between Example 2 and Example 1 is that the amino acid used in step (1) is (S)-phenylglycine protected by N-Boc, the reduction reaction temperature is 0°C, and the LiAlH used in step (2) 4 The amount is 16.2mmol, and other preparation steps and conditions are the same as in Example 1, and 1.45g of chiral secondary-tertiary amine compound of colorless oily liquid is finally obtained, with a total yield of 70%;

[0064] Its structural formula is: The absolute configuration is: S.

[0065] Data characterization of chiral secondary-tertiary amine compound 2: [α] D 20 =+26.1(c 1.5, CHCl 3 ).

[0066] 1 H NMR (400MHz, CDCl 3 ):δ7.37–7.30(m,4H),7.26–7.22(m,1H),3.53(dd,J=10.8Hz,J=3.6Hz,1H),2.70–2.61(m,2H),2.53– 2.41 (m, 5H), 2.29 (s, 3H), 1.02 (t, J=7.2Hz, 6H).

[0067] 13 C NMR (100MHz, CDCl 3): δ142.9, 128.3, 127.5, 127.0, 63.7, 61.3, 47.3, 34.8, 12.0.

[0068] HMRS(ESI): Theoretical [M+H] + C 13 h 23 N 2 is 207.1856, giving m / z 207.1856.

Embodiment 3

[0070] The difference between Example 3 and Example 1 is that the amino acid used in step (1) is N-Boc protected L-phenylalanine, the reduction reaction temperature is 50°C, and the LiAlH used in step (2) 4 The amount is 2.99g, 81mmol, and other preparation steps and conditions are the same as in Example 1, and 0.83g of the chiral secondary-tertiary amine product of a colorless oily liquid is finally obtained, with a total yield of 75%;

[0071] Its structural formula is: The absolute configuration is: S.

[0072] Data characterization of chiral acyclic secondary-tertiary amine compound 3: [α] D 20 =+80.8(c 1.2, CHCl 3 ).

[0073] 1 H NMR (400MHz, CDCl 3 ):δ7.27–7.25(m,2H),7.20–7.16(m,3H),2.85(dd,J=13.6Hz,J=5.2Hz,1H),2.72–2.66(m,1H),2.56– 2.45 (m, 4H), 2.43 (s, 3H), 2.40–2.34 (m, 2H), 2.32–2.25 (m, 2H), 0.94 (t, J=7.2Hz, 6H).

[0074] 13 C NMR (100MHz, CDCl 3 ): δ142.9, 128.3, 127.5, 127.0, 59.7, 57.1, 47.5, 39.2, 34.6, 12.0.

[0075] HMRS(ESI): Theoretical [M+H] ...

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Abstract

The invention relates to a chiral acyclic secondary amine-tertiary amine catalyst derived from amino acid and a preparation method and application thereof, and belongs to the technical field of catalysts. The catalyst has an acyclic secondary amine and a tertiary amine functional group, a structural formula is shown in the description; the catalyst is made of a cheap and easy-to-obtain alpha-aminoacid derivative, and a novel chiral acyclic secondary amine-tertiary amine compound is obtained through simple preparation steps; the catalyst can be used for catalyzing asymmetric Aldol reaction between acetaldehyde and isatin ketone, and can also be used for catalyzing asymmetric Mannich reaction between acetaldehyde or alpha-substituted aldehyde and isatin ketone; high catalytic activity and stereoselectivity are provided, diastereoselectivity is as high as 20:1, enantioselectivity is up to 96%, reaction substrates are wide, and the method is easy to popularize and apply.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a novel chiral acyclic secondary-tertiary amine catalyst derived from amino acids, a preparation method and a new application thereof. Background technique [0002] Chiral compounds play an important role in medicine, pesticides and functional materials, and their social demands are increasing day by day. Asymmetric catalytic synthesis is the most cost-effective method to obtain optically active compounds. In the study of asymmetric catalytic synthesis methodology, the design and synthesis of chiral catalysts is the most critical issue, and it is also one of the most active research fields in the world. Although many types of chiral catalysts have been synthesized, most catalysts have low catalytic efficiency and a large amount of catalyst, and many catalysts are only effective for specific reactions or even specific substrates, and are not universal. sex. Theref...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/02C07D209/38C07D209/40C07D295/13C07C209/68C07C211/09
CPCB01J31/0237B01J31/0244B01J2231/341C07B2200/07C07C211/09C07D209/38C07D209/40C07D295/13Y02P20/55
Inventor 邵志会代俊邓玉华
Owner YUNNAN UNIV
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