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Method for non-activated olefin benzylation synthesis of benzylation indoline compound

A technology of olefin benzyl and phenethyl indoline, applied in organic chemistry and other directions, can solve problems such as functional group intolerance, and achieve the effects of good tolerance, direct synthesis method and wide range of substrates

Pending Publication Date: 2019-05-17
KUNMING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] There are few examples of synthesizing indolines from acyclic starting materials, and the reduction of oxindoles to indolines faces serious functional group intolerance problems due to the strong reducing conditions required.

Method used

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  • Method for non-activated olefin benzylation synthesis of benzylation indoline compound
  • Method for non-activated olefin benzylation synthesis of benzylation indoline compound
  • Method for non-activated olefin benzylation synthesis of benzylation indoline compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Synthesis of non-activated olefins formula I compound (taking 1a2 synthesis as an example), the reaction scheme is as follows:

[0041]

[0042] Operation steps: Add p-toluidine (1.607g, 15.0mmol), CH 2 Cl 2 (50.0 mL), and Et 3 N (4.170 mL, 30.0 mmol) and finally acetyl chloride (1.273 mL, 18.0 mmol) was added. The reaction mixture was stirred at room temperature with a magnetic stirrer. TLC showed that after the raw material p-toluidine was consumed, it was washed with saturated NaHCO 3 solution (100 mL), the reaction was quenched with CH 2 Cl 2 (100.0 mL) was extracted 3 times. The combined organic phases were washed twice with brine (50 mL). The solid obtained by distilling off the organic solvent was washed with a mixture of petroleum ether / ethyl acetate (5:1, volume ratio) to obtain p-methylacetanilide (2.104 g, 94% yield) as a white solid. To a stirred solution of p-methylacetanilide (1.492 g, 10.0 mmol) and NaOH (600 mg, 15.0 mmol) in DMF (30 mL) was a...

Embodiment 2

[0047] Benzylation of non-activated olefins to synthesize benzylated indoline compounds (taking the synthesis of 2a1 as an example), the reaction scheme is as follows:

[0048]

[0049] Operation steps: add N-allyl aniline 1a1 (0.25mmol), MnCl 2 4H 2 O (5 mg, 0.025 mmol), DTBP (73 mg, 0.50 mmol) and solvent toluene (5.0 mL). The mixture was reacted at 140°C for 6h, then washed with saturated Na 2 S 2 o 3 (1.0 mL) and water (10.0 mL) and extracted three times with dichloromethane (10.0 mL). The residue obtained by evaporating the organic solvent was subjected to column chromatography (silica gel as stationary phase, petroleum ether and ethyl acetate as eluent) to obtain the benzylated indoline product 2a1.

[0050] With reference to the above-mentioned Example 2, investigate the influence of the catalyst on the reaction, the details are shown in Table 2 below.

[0051] Table 2 Catalyst's influence investigation on reaction [a]

[0052]

[0053]

[0054] [a] Re...

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PUM

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Abstract

The invention provides a method for non-activated olefin benzylation synthesis of a benzylation indoline compound. According to the method, indoline can be synthetized through a non-ring raw material,and meanwhile the performance tolerance of a functional group is good; the method is the first case to achieve a benzyl hydrogen C-H bond functionalized reaction of toluene and non-activated double-bonds; under the effects of cheap MnCl2.4H2O and di-tert-butyl peroxide (DTBP), N-allylaniline compounds generate a series-connection benzylation / cyclization reaction to generate the benzylation indoline, and the exo selectivity is shown; and the simple and direct synthesis method is provided for synthesis of the benzylation indoline, and the advantages of wide substrate range, easy operation and the like are achieved.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing benzylated indoline compounds through benzylation of non-activated olefins. Background technique [0002] Indolines are a very important class of nitrogen-containing heterocyclic compounds, which are commonly found in alkaloids and other natural products. They have huge applications in the dye industry, spices, organic intermediate synthesis, medicine, and pesticide synthesis. Due to the diverse biological activities and clinical applications of compounds with indoline as the core structure, scientists are in turn required to synthesize more structurally diverse indoline derivatives as drug lead molecules. However, in indole chemistry, the indoline skeleton is much more difficult to construct than other indole structures (such as oxindole) (Document 1: K.Nagarajua, D.Ma, Chem.Soc.Rev.2018, 47, 8018-8029; Literature 2: Z.Xu, Q.Wang,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/08C07D217/24C07D471/04
Inventor 梁德强李秀兰王宝玲李维莉马银海
Owner KUNMING UNIV
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