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3-vinyl indoline derivatives with optical activity and asymmetric synthesis method of same

A technology based on indolines and optical activity, applied in the field of 3-vinyl indoline derivatives and their asymmetric synthesis, can solve the problems of high operating cost, large functional group limitations, cumbersome steps, etc., and achieve high The effect of enantioselectivity

Inactive Publication Date: 2015-03-04
HUAZHONG NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these methods have their own characteristics and advantages, in general, there are disadvantages such as unavailable raw materials, limited functional groups, cumbersome steps, and high operating costs.

Method used

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  • 3-vinyl indoline derivatives with optical activity and asymmetric synthesis method of same
  • 3-vinyl indoline derivatives with optical activity and asymmetric synthesis method of same
  • 3-vinyl indoline derivatives with optical activity and asymmetric synthesis method of same

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Compound I-1

[0027] preparation of

[0028] At room temperature, the metal catalyst tris(dibenzylideneacetone)dipalladium chloroform adduct (10.35mg, 0.01mmol) and ligand IV (12.6mg, 0.022mmol) were dissolved in chloroform and stirred for 20 minutes under nitrogen protection , and then cooled to -40 degrees Celsius. Then add 4-vinylbenzoxazinone II-1 (66mg, 0.2mmol), continue to stir at -40 degrees Celsius for 5 minutes, then add sulfur ylide III-1 (54mg, 0.3mmol) to the reaction system , the reaction mixture continues to react at -40°C until TLC detects that the reaction is complete, with V 石油醚 / V 乙酸乙酯 =30:1-12:1 Column chromatography directly obtained 80.7 mg of the target product of formula I-1, with a yield of 99%.

[0029] 1 H NMR (600MHz, CDCl 3 )δ (ppm) = 8.00 (d, J = 7.5Hz, 2H), 7.75 (d, J = 8.0Hz, 2H), 7.62 (t, J = 9.6Hz, 2H), 7.50 (t, J = 7.6Hz ,2H),7.27(d,J=7.8Hz,3H),7.02(t,J=7.2Hz,1H),6.97(d,J=7.4Hz,1H),5.44–5.35(m,1H),5.32 (d, J = 4.9Hz, 1H), 4....

Embodiment 2

[0036] Compound I-2

[0037] preparation of

[0038] At room temperature, metal catalyst tris(dibenzylideneacetone)dipalladium chloroform adduct (10.35mg, 0.01mmol) and ligand IV (12.6mg, 0.022mmol) were dissolved in chloroform, under nitrogen protection Stir for 20 minutes, then cool down to -40 degrees Celsius. Then add 4-vinylbenzoxazinone II-1 (66mg, 0.2mmol), continue to stir at -40 degrees Celsius for 5 minutes, then add sulfur ylide III-2 (63mg, 0.3mmol) to the reaction system , the reaction mixture continues to react at -40°C until TLC detects that the reaction is complete, with V 石油醚 / V 乙酸乙酯 =30:1-12:1 column chromatography directly obtained 86.6 mg of the target product of formula I-2, with a yield of 99%.

[0039] 1 H NMR (600MHz, CDCl 3)δ (ppm) = 7.98 (d, J = 8.5Hz, 2H), 7.74 (d, J = 7.9Hz, 2H), 7.64 (d, J = 8.0Hz, 1H), 7.25 (d, J = 7.2Hz ,3H),7.03–6.97(m,1H),6.95(d,J=8.3Hz,3H),5.39-5.33(m,1H),5.29(d,J=4.7Hz,1H),5.00-4.92( m,2H), 3.85(s,3H), 3.79-3.76(m,1...

Embodiment 3

[0046] Compound I-3

[0047] preparation of

[0048] At room temperature, metal catalyst tris(dibenzylideneacetone)dipalladium chloroform adduct (10.35mg, 0.01mmol) and ligand IV (12.6mg, 0.022mmol) were dissolved in chloroform, under nitrogen protection Stir for 20 minutes, then cool down to -40 degrees Celsius. Then add 4-vinylbenzoxazinone II-1 (66mg, 0.2mmol), continue to stir at -40 degrees Celsius for 5 minutes, then add sulfur ylide III-3 (60mg, 0.3mmol) to the reaction system , the reaction mixture continues to react at -40°C until TLC detects that the reaction is complete, with V 石油醚 / V 乙酸乙酯 =30:1-12:1 column chromatography directly obtained 74.6 mg of the target product of formula I-3, with a yield of 92%.

[0049] 1 H NMR (600MHz, CDCl 3 )δ (ppm) = 7.90 (d, J = 7.2Hz, 2H), 7.74 (d, J = 7.2Hz, 2H), 7.64 (d, J = 7.9Hz, 1H), 7.29-7.25 (m, 5H) ,7.04–6.92(m,2H),5.41-5.37(m,1H),5.32(s,1H),4.97(dd,J=21.5,13.4Hz,2H),3.78(s,1H),2.42(s ,3H), 2.38(s,3H).

[0050] 1...

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Abstract

The invention relates to 3-vinyl indoline derivatives with optical activity and an asymmetric synthesis method of the same. The 3-vinyl indoline derivatives have a structural formula as shown in a general formula I (described in the specification), wherein R1 is hydrogen, 4-fluorine, 5-methyl, 5-methoxyl, 5-bromine, 6-chlorine and 7-fluorine; and R2 is phenyl, p-methoxyphenyl, p-methylphenyl, p-fluorophenyl, p-chlorphenyl, o-fluorophenyl, m-bromophenyl, 2-thiophene, 2-furan, ethyoxyl, styryl and isobutyl. The synthesis method of the 3-vinyl indoline derivatives comprises the step of carrying out a decarboxylation allylation / cyclizing series reaction on compounds which are as shown in a general formula II and a general formula III in a chloroform solvent in presence of a metal catalyst tris(dibenzylideneacetone) dipalladium chloroform adduct and a ligand IV. The synthesis method of the 3-vinyl indoline derivatives has the advantages that a cycloaddition manner is adopted, the 3-vinyl indoline derivatives with the optical activity can be efficiently synthesized with high enantioselectivity through one-step operation only, the yield is 63-99%, dr is more than 99.5% and ee is 83-99%.

Description

technical field [0001] The invention relates to optically active 3-vinylindoline derivatives and an asymmetric synthesis method thereof. Background technique [0002] Indoline derivatives are an extremely important class of heterocyclic compounds, which widely exist in a variety of natural products and drug molecules, and their wide range of biological activities have attracted more and more interest of chemists. [0003] [0004] Efficient and highly selective synthetic methods of indoline compounds have been widely concerned by chemists. The traditional methods for synthesizing optically active indoline skeletons mainly include the following three methods: the resolution of racemic indoline, the asymmetric hydrogenation of indole compounds, and the synthesis of halogen-substituted arylamines. Compound coupling reactions. Although these methods have their own characteristics and advantages, in general, there are disadvantages such as unavailable raw materials, limited ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/12C07D409/06C07D405/06C07D209/42C07D498/04
CPCC07B2200/07C07D209/12C07D209/42C07D405/06C07D409/06C07D498/04
Inventor 肖文精李天任谭芬陆良秋陈加荣
Owner HUAZHONG NORMAL UNIV
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