CN110452151B - Synthetic method of alpha-indole glycine derivative - Google Patents
Synthetic method of alpha-indole glycine derivative Download PDFInfo
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a synthesis method of an alpha-indole glycine derivative, which comprises the steps of taking a glycine derivative and substituted indole as raw materials, taking acetonitrile as a solvent, taking organic dye rose bengal as a photosensitive catalyst, and carrying out one-step synthesis on the corresponding indole glycine derivative by illumination at room temperature and in air. The synthetic method is green and environment-friendly, toxic catalysts are not needed, and the used catalysts are cheap and low in dosage, so that the production cost is effectively reduced; secondly, the operation is convenient, heating and inert gas protection are not needed, the reaction can be carried out only at room temperature, in the air and under the illumination condition, and the method is suitable for large-scale production; finally, the yield of the target compound is high, and the substrate range is wide.
Description
Technical Field
The invention relates to a synthetic method of an alpha-indole glycine derivative, belonging to the technical field of organic synthesis.
Background
Alpha-indolylglycine derivatives are important organic synthetic intermediates and have very wide applications in the fields of natural products and medicine, for example: the derivatives etodolac (etodolac) and pemetrexed (pemedolac) have significant anti-inflammatory activity, and are widely used for treating postoperative pain and have analgesic and anti-inflammatory effects clinically. Therefore, the development of new method and technology for synthesizing the alpha-indole glycine derivative has important research significance.
The synthesis of α -indoleglycine derivatives, commonly used in the early days, was mainly obtained by catalytic Mannich-type Friedel-Crafts reaction of indole and imine (synthesis, 2005, 13, 2198-2204). In recent years, cross-dehydrogenation coupling reaction (cross-dehydrogenation coupling) has unique advantages in constructing carbon-carbon bonds, and alpha-indole glycine derivatives are directly constructed by means of cross-dehydrogenation coupling between C-H at the 3-position of indole and C-H at the alpha-position of glycine derivative nitrogen, so that the method also becomes an efficient method for synthesizing the alpha-indole glycine derivatives at present.
However, the traditional mannich friedel-crafts reaction needs imine as a reaction raw material, and the imine is unstable in air and easy to hydrolyze; the existing cross dehydrogenation coupling method usually needs copper or iron metal as a catalyst or organic strong oxidant, pure oxygen phenol, ruthenium or iridium as a photosensitive catalyst, wherein the metal catalyst such as copper is easy to have the problem of metal residue, the photosensitive catalyst such as ruthenium is expensive, and a large amount of organic peroxide and oxygen phenol are used, so that certain potential safety hazard exists. Therefore, the application of the above synthetic method has a certain limitation.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a synthetic method of an alpha-indole glycine derivative, and the synthetic method is environment-friendly, simple and convenient to operate, mild in reaction condition, low in production cost and high in yield.
The invention content is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a synthesis method of an alpha-indole glycine derivative comprises the steps of taking a glycine derivative and substituted indole as raw materials, taking acetonitrile as a solvent, taking an organic dye rose bengal as a photosensitive catalyst, and synthesizing the corresponding indole glycine derivative in one step by illumination at room temperature and under the air condition.
Wherein, the adding molar ratio of the glycine derivative to the substituted indole is 1: 1.
Wherein the addition amount of rose bengal in the reaction system is 1mol%.
Wherein, the illumination condition is as follows: irradiating and reacting for 12-13 hours under the blue light with the light intensity not lower than 34W.
Wherein, the structural general formula of the glycine derivative is:
R 1 hydrogen, halogen or alkoxy which is monosubstituted at the para position of a benzene ring; r 2 Is alkyl or benzyl.
Wherein, the structural general formula of the substituted indole is:
R 3 at any position of the benzene ring, hydrogen, alkyl or halogen; r 4 Is hydrogen or methyl.
Wherein, the structural general formula of the synthesized indole glycine derivative is as follows:
R 1 hydrogen, halogen or alkoxy which is monosubstituted at the para position of a benzene ring; r 2 Is alkyl or benzyl; r is 3 At any position of the benzene ring, hydrogen, alkyl or halogen; r 4 Is hydrogen or methyl.
The reaction formula of the synthetic method is as follows:
the method adopts organic dye rose bengal as a catalyst, under the irradiation of visible light, the rose bengal is excited to an excited state, then a single electron is transferred from a glycine ester derivative to an excited rose bengal molecule to form a corresponding glycine derivative cation radical intermediate and a rose bengal anion radical, the rose bengal radical is transferred to oxygen in the air to form an oxygen anion radical and a rose bengal molecule, so that the catalyst circulates, and finally the oxygen anion radical takes one hydrogen atom on the glycine derivative cation radical intermediate to form active imine positive ions to react with an indole nucleophilic reagent, thereby obtaining a final product.
Has the advantages that: the synthetic method of the invention overcomes the problems of high production cost, serious environmental pollution, use of toxic catalyst, heavy metal residue, large danger coefficient, harsh reaction conditions and the like in the existing method for synthesizing the alpha-indole glycine derivative; secondly, the operation is convenient, heating and inert gas protection are not needed, the reaction can be carried out only at room temperature, in the air and under the illumination condition, and the method is suitable for large-scale production; finally, the yield of the target compound is high, and the substrate range is wide.
Drawings
FIG. 1 is a NMR chart of an α -indolylglycine derivative obtained in example 1 of the present invention;
FIG. 2 is a carbon spectrum of an α -indolylglycine derivative obtained in example 1 of the present invention;
FIG. 3 is a mass spectrum of an α -indolylglycine derivative obtained in example 1 of the present invention;
FIG. 4 is a NMR chart of an α -indolylglycine derivative obtained in example 2 of the present invention;
FIG. 5 is a carbon spectrum of an α -indolylglycine derivative obtained in example 2 of the present invention;
FIG. 6 is a mass spectrum of an α -indolylglycine derivative obtained in example 2 of the present invention;
FIG. 7 is a NMR chart of an α -indole glycine derivative obtained in example 3 of the present invention;
FIG. 8 is a carbon spectrum of an α -indolylglycine derivative obtained in example 3 of the present invention;
FIG. 9 is a mass spectrum of an α -indolylglycine derivative obtained in example 3 of the present invention;
FIG. 10 is a NMR chart of an α -indole glycine derivative obtained in example 4 of the present invention;
FIG. 11 is a carbon spectrum of an α -indolylglycine derivative obtained in example 4 of the present invention;
FIG. 12 is a mass spectrum of an α -indolylglycine derivative obtained in example 4 of the present invention;
FIG. 13 is a NMR chart of an α -indole glycine derivative obtained in example 5 of the present invention;
FIG. 14 is a carbon spectrum of an α -indolylglycine derivative obtained in example 5 of the present invention;
FIG. 15 is a mass spectrum of an α -indolylglycine derivative obtained in example 5 of the present invention;
FIG. 16 is a NMR chart of an α -indolylglycine derivative obtained in example 6 of the present invention;
FIG. 17 is a carbon spectrum of an α -indolylglycine derivative obtained in example 6 of the present invention;
FIG. 18 is a mass spectrum of an α -indolylglycine derivative obtained in example 6 of the present invention;
FIG. 19 is a NMR spectrum of an α -indolylglycine derivative obtained in example 7 of the present invention;
FIG. 20 is a carbon spectrum of an α -indolylglycine derivative obtained in example 7 of the present invention;
FIG. 21 is a mass spectrum of an α -indolylglycine derivative obtained in example 7 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following specific examples.
All the following reagents used in the examples are commercially available, and the required reagents such as ethyl bromoacetate, p-anisidine, ethanol, sodium acetate, substituted indoles, acetonitrile, rose bengal (Rose bengal) are commercially available from ann naige, taitan science and others.
Various glycine derivatives can be prepared by the prior art using corresponding commercial reagents, such as ethyl bromoacetate and p-methylaniline as raw materials and sodium acetate as a catalyst, and reacting in ethanol solution (eur.j.org.chem., 2006, 76, 3766).
Example 1
1a (0.209g, 1.0 mmol), indole 2a (0.117g, 1.0 mmol), rose bengal (0.010 g) and 10mL CH3CN were added to a 25mL colorimetric tube, and the mixture was stirred at room temperature in the air, and irradiated with Blue light (Blue LED) having a light intensity of 34W for 12 hours, after which the reaction solution was subjected to column chromatography (petroleum ether: ethyl acetate = 5: 1) to obtain 3aa, 0.262g.
Indole glycine derivative 3aa: the yield is 81%; 1 H NMR(400MHz，CDCl 3 )δ8.42(s，1H)，7.88(d，J＝7.7Hz，1H)，7.35-7.31(m，1H)，7.23(dtd，J＝14.6，7.0，1.2Hz，2H)，7.16(d，J＝2.5Hz，1H)，6.84-6.79(m，2H)，6.70-6.65(m，2H)，5.39(s，1H)，4.55(s，1H)，4.30(dq，J＝10.8，7.1Hz，1H)，4.17(dq，J＝10.8，7.1Hz，1H)，3.77(s，3H)，1.25(t，J＝7.1Hz，3H). 13 C NMR(101MHz，CDCl 3 )δ173.02，152.61，140.88，136.52，125.85，123.20，122.48，120.00，119.50，114.96，112.55，111.53，61.57，55.77，55.33，14.18.MS(ESI)m/z calcd for C 19 H 20 N 2 O 3 (M-H) + ＝323.15，found＝323.1.
example 2
To a 25mL cuvette were added 1b (0.179g, 1.0mmol), indole 2a (0.117g, 1.0mmol), rose bengal (0.010 g) and 10mL CH 3 CN, stirring at room temperature in air, placing the mixture under Blue light (Blue LED) with the light intensity of 34W for irradiation reaction for 12 hours, and after the reaction, performing column chromatography separation on the reaction liquid (petroleum ether: ethyl acetate = 5: 1) to obtain a product, namely, 3ba, 0.202g.
Indole glycine derivative 3ba: the yield is 69%; 1 H NMR(400MHz，CDCl 3 )δ8.23(s，1H)，7.88(d，J＝7.8Hz，1H)，7.38-7.34(m，1H)，7.27(d，J＝1.1Hz，1H)，7.24-7.17(m，4H)，6.81-6.76(m，1H)，6.69(dd，J＝8.6，0.9Hz，2H)，5.45(s，1H)，4.81(s，1H)，4.31(dq，J＝10.8，7.1Hz，1H)，4.17(tt，J＝7.1，5.1Hz，1H)，1.26(t，J＝7.1Hz，3H). 13 C NMR(101MHz，CDCl 3 )δ172.73，146.62，136.54，129.31，125.82，123.21，122.54，120.04，119.56，118.16，113.47，112.46，111.50，61.66，54.36，14.16.MS(ESI)m/z calcd for C 18 H 18 N 2 O 2 (M-H) + ＝293.14，found＝293.1.
example 3
To a 25mL colorimetric cylinder were added 1c (0.213g, 1.0 mmol), indole 2a (0.117g, 1.0 mmol), rose bengal (0.010 g) and 10mL CH 3 CN, stirring at room temperature under air condition, placing the mixture under Blue light (Blue LED) with light intensity of 34W for irradiation reaction for 12 hours, and performing column chromatography separation (petroleum ether: ethyl acetate = 5: 1) on the reaction liquid after the reaction to obtain a product of 3ca 0.209g.
Indole glycine derivative 3ca: the yield is 64%; 1 H NMR(400MHz，CDCl 3 )δ8.22(s，1H)，7.84(d，J＝7.9Hz，1H)，7.42-7.38(m，1H)，7.28(dd，J＝6.5，1.6Hz，1H)，7.24-7.18(m，2H)，7.14-7.08(m，2H)，6.60-6.54(m，2H)，5.37(d，J＝4.8Hz，1H)，4.84(d，J＝4.7Hz，1H)，4.30(dq，J＝10.8，7.1Hz，1H)，4.21-4.12(m，1H)，1.25(t，J＝7.1Hz，3H). 13 C NMR(101MHz，CDCl 3 )δ172.29，145.07，136.53，129.08，125.74，123.10，122.67，120.16，119.51，114.52，112.23，111.46，61.75，54.32，14.14.MS(ESI)m/z calcd for C 18 H 17 ClN 2 O 2 (M-H)+＝327.1，found＝327.1.
example 4
To a 25mL colorimetric tube were added 1d (0.271g, 1.0 mmol), indole 2a (0.117g, 1.0 mmol), rose bengal (0.010 g), and 10mL CH 3 CN, stirring at room temperature under air condition, placing the mixture under Blue light (Blue LED) with the light intensity of 34W for irradiation reaction for 12 hours, and performing column chromatography separation (petroleum ether: ethyl acetate = 5: 1) on the reaction liquid after the reaction to obtain the product of 3da 0.288g.
Indole glycine derivative 3da: the yield is 75%; 1 H NMR(400MHz，CDCl 3 )δ8.24(s，1H)，7.84(d，J＝7.9Hz，1H)，7.37(d，J＝8.1Hz，1H)，7.33-7.29(m，3H)，7.28-7.21(m，3H)，7.20-7.14(m，2H)，6.77(dd，J＝9.5，2.7Hz，2H)，6.65(dd，J＝9.5，2.7Hz，2H)，5.44(s，1H)，5.27(d，J＝12.3Hz，1H)，5.13(d，J＝12.3Hz，1H)，4.53(s，1H)，3.76(s，3H). 13 C NMR(101 MHz，CDCl 3 )δ172.78，152.66，140.77，136.46，135.48，128.48，128.23，125.85，123.11，122.58，120.09，119.56，114.95，112.49，111.43，67.12，55.76，55.35.MS(ESI)m/z calcd for C 24 H 22 N 2 O 3 (M-H) + ＝385.16，found＝385.1.
example 5
To a 25mL colorimetric cylinder were added 1a (0.209g, 1.0mmol), indole 2b (0.131g, 1.0mmol), rose bengal (0.010 g) and 10mL CH 3 CN, stirring at room temperature in the air, placing the mixture under Blue light (Blue LED) with the light intensity of 34W for irradiation reaction for 12 hours, and after the reaction, performing column chromatography separation on the reaction liquid (petroleum ether: ethyl acetate = 5: 1) to obtain a product, namely, 3ab, 0.263g.
Indole glycine derivative 3ab: the yield is 78%; 1 H NMR(400MHz，CDCl 3 )δ7.88(d，J＝8.0Hz，1H)，7.32(dt，J＝8.1，4.4Hz，2H)，7.24-7.19(m，1H)，7.16(s，1H)，6.82-6.78(m，2H)，6.70-6.65(m，2H)，5.37(s，1H)，5.37(s，1H)，4.31(dq，J＝10.8，7.1Hz，1H)，4.21-4.13(m，1H)，3.77(s，6H)，1.27(t，J＝7.1Hz，3H). 13 C NMR(101MHz，CDCl 3 )δ172.92，152.53，140.91，137.32，127.59，126.37，122.07，119.69，119.57，114.84，111.17，109.52，61.48，55.74，55.18，32.88，14.19.MS(ESI)m/z calcd for C 20 H 22 N 2 O 3 (M-H) + ＝337.16，found＝337.3.
example 6
To a 25mL colorimetric cylinder were added 1a (0.209g, 1.0mmol), indole 2c (0.151g, 1.0mmol), rose bengal (0.010 g) and 10mL CH 3 CN, stirring at room temperature in air, placing the mixture under Blue light (Blue LED) with the light intensity of 34W for irradiation reaction for 12 hours, and performing column chromatography separation (petroleum ether: ethyl acetate = 5: 1) on the reaction liquid after the reaction to obtain a product, namely, 3ac 0.246g.
Indole glycine derivative 3ac: the yield is 69%; 1 H NMR(400MHz，CDCl 3 )δ8.40(s，1H)，7.84(d，J＝1.8Hz，1H)，7.25(d，J＝8.6Hz，1H)，7.21-7.16(m，2H)，6.81-6.76(m，2H)，6.66-6.61(m，2H)，5.29(s，1H)，4.59-4.40(m，1H)，4.28(dq，J＝10.8，7.1Hz，1H)，4.17(dq，J＝10.8，7.1Hz，1H)，3.75(s，3H)，1.25(t，J＝7.1Hz，3H). 13 C NMR(101 MHz，CDCl 3 )δ172.63，152.67，140.58，134.89，126.87，125.76，124.50，122.84，119.12，114.95，112.50，61.75，55.75，55.13，14.13.MS(ESI)m/z calcd for C 20 H 21 ClN 2 O 3 (M-H) + ＝357.11，found＝357.0.
example 7
To a 25mL colorimetric cylinder were added 1a (0.209g, 1.0 mmol), indole 2d (0.131g, 1.0 mmol), rose bengal (0)010 g) and 10mL CH 3 CN, stirring at room temperature in air, placing the mixture under Blue light (Blue LED) with the light intensity of 34W for irradiation reaction for 12 hours, and after the reaction, performing column chromatography separation on the reaction liquid (petroleum ether: ethyl acetate = 5: 1) to obtain a product 3ad 0.242g.
Indole glycine derivative 3ad: the yield is 72%; 1 H NMR(400MHz，CDCl 3 )δ8.21(s，1H)，7.75(d，J＝8.1Hz，1H)，7.14-7.10(m，2H)，7.04(d，J＝8.3Hz，1H)，6.82-6.77(m，2H)，6.68-6.63(m，2H)，5.35(s，1H)，4.52(s，1H)，4.29(dq，J＝10.8，7.1Hz，1H)，4.16(dq，J＝10.8，7.1Hz，1H)，3.76(s，3H)，2.49(s，3H)，1.25(t，J＝7.1Hz，3H). 13 C NMR(101 MHz，CDCl 3 )δ172.98，152.56，140.91，136.99，132.34，123.68，122.51，121.77，119.16，114.90，112.44，111.41，61.50，55.75，55.37，21.69，14.18.MS(ESI)m/z calcd for C 20 H 22 N 2 O 3 (M-H) + ＝337.16，found＝337.2.
Claims (1)
1. a synthetic method of alpha-indole glycine derivatives is characterized in that: the synthesis method comprises the steps of taking glycine derivatives and substituted indoles as raw materials, taking acetonitrile as a solvent, taking rose bengal as a photosensitive catalyst, and synthesizing the corresponding indole glycine derivatives in one step by illumination at room temperature and in air;
wherein, the structural general formula of the glycine derivative is:
R 1 hydrogen, halogen or alkoxy which is monosubstituted at the para position of a benzene ring; r 2 Is alkyl or benzyl;
the structural general formula of the substituted indole is as follows:
R 3 at any position of the benzene ring, hydrogen, alkyl or halogen; r 4 Is hydrogen or methyl;
the structural general formula of the synthesized indole glycine derivative is as follows:
R 1 hydrogen, halogen or alkoxy which is monosubstituted at the para position of a benzene ring; r 2 Is alkyl or benzyl; r 3 At any position of the benzene ring, hydrogen, alkyl or halogen; r is 4 Is hydrogen or methyl;
the addition molar ratio of the glycine derivative to the substituted indole is 1, the addition amount of the rose bengal in the reaction system is 1mol%, and the illumination conditions are as follows: the reaction is carried out for 12 to 13 hours under the irradiation of blue light with the light intensity not less than 34W.
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| Direct α‑Arylation of α‑Amino Carbonyl Compounds with Indole Using Visible Light Photoredox Catalysis;Zhi-Qiang Wang，等;《J. Org. Chem.》;20120917;8705-8711 * |
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