Asymmetric cyclopropanation method of copper-catalyzed olefin and application of asymmetric cyclopropanation method

A technology for cyclopropanation and catalysis of olefins, which is applied in catalytic reactions, asymmetric synthesis, organic chemical methods, etc., can solve problems such as low selectivity, narrow reaction substrate range, and difficulty in industrial application, achieving high selectivity and easy operation. Simple and cheap catalyst effect

Inactive Publication Date: 2021-05-21
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this method also has many limitations, such as a narrow range of reaction substrates, low selectivity, and difficulty in industrial application.

Method used

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  • Asymmetric cyclopropanation method of copper-catalyzed olefin and application of asymmetric cyclopropanation method
  • Asymmetric cyclopropanation method of copper-catalyzed olefin and application of asymmetric cyclopropanation method
  • Asymmetric cyclopropanation method of copper-catalyzed olefin and application of asymmetric cyclopropanation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Copper-catalyzed asymmetric cyclopropanation of alkenes: under the protection of nitrogen, the metallic copper precursor CuOTf 0.5C 6 h 6 (5mol%) and chiral P,N,N-ligand L-1-1 (5.5mol%) were placed in a 25mL Scheurunk tube, added 1mL dichloroethane, and stirred at room temperature for 2h in situ coordination to obtain hand copper catalyst. Dissolve the substrate cis-β-methylstyrene II-1 in 1 mL of dichloroethane, add it to the above stirred chiral copper catalyst solution, add the newly activated Molecular sieves, after stirring at 60°C for 0.5 hours, slowly add the diazo compound III-1 with a syringe pump, the dropwise addition is completed in 8 hours, and the reaction is continued for 10 hours. After completion of the reaction, filter, concentrate under reduced pressure to almost no solvent, separate by silica gel column chromatography, concentrate under reduced pressure, and dry in vacuo to obtain the cyclopropanated product I-1 with a yield of 95%, dr>19:1, and 9...

Embodiment 2

[0036] L-1-2 reacts as a ligand to generate product I-1

[0037] The ligand L-1-1 in Example 1 is replaced by the ligand L-1-2, and the rest are the same as in Example 1. The reaction yielded compound I-1 in 87% yield, dr=16:1, 75% ee.

[0038] The structural formula of L-1-2 is as follows:

[0039]

Embodiment 3

[0041] L-1-3 reacts as a ligand to generate product I-1

[0042] The ligand L-1-1 in Example 1 is replaced by the ligand L-1-3, and the rest are the same as in Example 1. The reaction gave compound I-1 in 50% yield, dr=16:1, 70% ee.

[0043] The structural formula of L-1-3 is as follows:

[0044]

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Abstract

The invention discloses an asymmetric cyclopropanation method of copper-catalyzed olefin and application thereof. The copper catalyst adopted by the method is generated in situ from a metal copper precursor and a chiral P, N, N-ligand in a reaction medium. The method has the characteristics of cheap catalyst, simple ligand preparation, high activity, high selectivity, mild reaction conditions, simple operation and the like, can realize continuous operation, and is suitable for large-scale industrial production. The method is also suitable for asymmetric synthesis of chiral first chrysanthemic acid which is an important intermediate of pyrethroid pesticides, the yield can reach 80%, the enantioselectivity can reach 85%, and the method can be applied to industrial preparation.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and specifically relates to copper / chiral P,N,N-ligand catalyzed asymmetric cyclopropanation reaction of alkenes, and also relates to the method in chiral pyrethroid insecticide key intermediate-chiral Application of the first asymmetric synthesis of chrysanthemic acid. Background technique [0002] Cyclopropane structures widely exist in carbocyclic and heterocyclic compounds with important biological activities, such as chiral pyrethroid insecticides. In addition, cyclopropane is also a very important class of synthetic intermediates, such as synthesizing mesocyclic compounds and functionalized molecules through ring-opening or ring-expanding strategies [(a) R.Faust, Angew.Chem.Int.Ed.2001,40 , 2251-2253; (b) H. Staudinger, L. Ruzicka, Helv. Chim. Acta 1924, 7, 177-235; (c) J. Pietruszka, Chem. Rev. 2003, 103, 1051-1070; (d) L.A. Wessjohann, W. Brandt, T. Thiemann, Chem. Rev. 2003, 103, 1625-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/347C07C69/743C07C69/747B01J31/24B01J31/22B01J31/18C07B53/00
CPCB01J31/189B01J31/2295B01J31/2404B01J2231/325B01J2531/0225B01J2531/0261B01J2531/16B01J2531/842C07B53/00C07B2200/07C07C67/347C07C2601/02C07C69/743C07C69/747
Inventor 胡向平刘振婷
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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