Synthetic method for derivatization of alpha-C (sp3)-H bond of cyclopropane compound

A synthesis method and compound technology, applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., can solve the problems of complex reaction steps, unfriendly environment, harsh synthesis reaction conditions, etc.

Pending Publication Date: 2022-04-12
TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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Problems solved by technology

[0005] The invention provides a simple and efficient organic rare earth catalyzed cyclopropane compound α-C(sp 3 )-H bond derivatization synthesis method to solve the technical problems such as harsh synthetic reaction conditions, complex reaction steps, and environmental unfriendliness in the prior art

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  • Synthetic method for derivatization of alpha-C (sp3)-H bond of cyclopropane compound
  • Synthetic method for derivatization of alpha-C (sp3)-H bond of cyclopropane compound
  • Synthetic method for derivatization of alpha-C (sp3)-H bond of cyclopropane compound

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[0029] One embodiment of the present invention proposes a cyclopropane compound α-C(sp 3 )-H bond derivatized synthetic method, comprising the steps:

[0030] Under the protection of an inert gas, in an organic solvent, the compound having the structure shown in the formula (I-1) reacts with the compound of the formula (II) under the action of a catalyst and a cocatalyst to obtain a compound having the structure of the compound of the formula (III-1) ;

[0031] Or, under the protection of an inert gas, in an organic solvent, the compound having the structure shown in formula (I-2) reacts with the compound of formula (II) under the action of catalyst and cocatalyst to obtain the compound structure of formula (III-2) compound of;

[0032] The catalyst is an organic rare earth compound; the cocatalyst is a boron salt;

[0033]

[0034] Among them, R 2 for R 1 The ortho-substitution, meta-substitution or para-substitution;

[0035] R 1 , R 2 independently selected from ...

Embodiment 1

[0056] A cyclopropane compound α-C(sp 3 )-H bond derivatized synthetic method, comprising the steps:

[0057] Under nitrogen atmosphere, the catalyst (η 2 -N-P-Ph 2 )Ln(CH 2 C 6 h 4 NMe 2 -o) 2 (28.8mg, 0.04mmol) was dissolved in 1mL chlorobenzene solvent and was added to a 50mL storage bottle for continuous stirring, and the promotor [Ph 3 C][B(C 6 f 5 ) 4 ] (36.9mg, 0.04mmol) was dissolved in 1mL of chlorobenzene solvent and slowly added dropwise to the chlorobenzene solution of the catalyst, then 2-cyclopropyl-6 ethyl-pyridine (147mg, 1.0mmol), 1-octene (448mg, 4.0mmol) was added into the reaction system, and a 50mL storage bottle was placed in a parallel reactor at 100°C to stir the reaction. The reaction was monitored by TLC. After the reaction was completed, it was cooled to room temperature, and the pure product was separated through a silica gel chromatography column (the mobile phase was 2% ethyl acetate in hexane), and the yield was 93%.

[0058] NMR ch...

Embodiment 2

[0060] A cyclopropane compound α-C(sp 3 )-H bond derivatized synthetic method, comprising the steps:

[0061] Under nitrogen atmosphere, the catalyst (η 2 -N-P-Ph 2 )Ln(CH 2 C 6 h 4 NMe 2 -o) 2 (28.8mg, 0.04mmol) was dissolved in 1mL chlorobenzene solvent and was added to a 50mL storage bottle for continuous stirring, and the promotor [Ph 3 C][B(C 6 f 5 ) 4 ] (36.9mg, 0.04mmol) was dissolved in 1mL of chlorobenzene solvent and slowly added dropwise to the chlorobenzene solution of the catalyst, then 2-cyclopropyl-6-isopropyl-pyridine ((161mg, 1.0mmol), 1 -Octene (448mg, 4.0mmol) joins in the reaction system, and 50mL liquid storage bottle is placed in the parallel reactor of 100 ℃ and stirs reaction.Reaction is monitored with TLC, is cooled to room temperature after completion of reaction, passes through silica gel chromatographic column (flow 2% ethyl acetate in hexane) to isolate the pure product with a yield of 91%.

[0062] NMR characterization is as follows:...

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Abstract

The invention provides a synthetic method for derivatization of alpha-C (sp3)-H bonds of cyclopropane compounds, and belongs to the technical field of synthesis. The synthesis method comprises the following steps: under the protection of inert gas, reacting a compound with a structure as shown in a formula (I-1) with a compound with a structure as shown in a formula (II) in an organic solvent under the action of a catalyst and a cocatalyst to obtain a compound with a structure as shown in a formula (III-1), or under the protection of inert gas, in an organic solvent, the compound with the structure as shown in the formula (I-2) reacts with the compound with the structure as shown in the formula (II) under the action of a catalyst and a cocatalyst to obtain the compound with the structure as shown in the formula (II-2), the raw materials needed by the method are cheap, easy to obtain and few in variety, the double-bond substituted carbocyclic derivatives with different structures can be obtained by changing substituent groups on the raw materials, and the raw materials are wide in application range. The compound synthesized by the method can be widely applied to the field of pharmaceutical chemicals.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a cyclopropane compound α-C(sp 3 )-H bond derivatization synthetic method. Background technique [0002] Due to their unique spatial, electronic and conformational characteristics, cyclopropanes have become attractive pharmacophores in medicinal chemistry, effective intermediates in synthetic chemistry and efficient ligands in catalysis, how to synthesize them simply and efficiently Cyclopropane and its derivatives have always been one of the research hotspots. [0003] Cyclopropane C(sp 3 The carbon-hydrogen activation of )-H bonds is one of the effective methods for the synthesis of cyclopropane derivatives. 3 )-H bond carbon-hydrogen activation has been greatly developed, for example, in 2011, Jin-QuanYu (J.Am.Chem.Soc.2011,133,19598–19601.) et al reported the realization of Cyclopropanes β-C(sp 3 )-H bond alkylation method; in 2019, Senmiao Xu et al. (J.Am.Chem...

Claims

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Application Information

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IPC IPC(8): C07D213/06C07D213/127C07C41/30C07C43/21
Inventor 陈延辉张美李永瑞周小涵陆超
Owner TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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