CN108003160B - Method for synthesizing [ a ] -cyclized indole derivative - Google Patents
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- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
The invention discloses a method for synthesizing [ a ] -cyclic indole compounds. Under the action of a palladium catalyst, norbornene is used as a transient guide medium, dihaloalkane is used as an alkylation reagent, and under the action of alkali, alkylation at the C2 position of substituted indole and N-H ring-closing domino reaction are successively realized by one pot, so that the [ a ] -ring-substituted indole compound is effectively synthesized. The method has mild conditions, directly uses commercially available substituted indole as a substrate, omits a pre-functionalization process, reduces reaction steps, has high atom economy, modifies a simple small molecular structure of the indole, can be further used for researches such as medicines or total synthesis, and has high potential value and wide application prospect in the fields of pharmaceutical chemistry and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a method for synthesizing [ a ] -cyclized indole derivatives.
Background
Many biologically active natural and non-natural compounds contain indole backbones. For example, indole alkaloids account for a quarter of the many alkaloids. Indole compounds are used as an important organic compound and widely applied to the fields of medicines, pesticides, foods, feed additives, dye industry and the like. [a] The core structure of the cyclized indole is present in a plurality of indole derivatives with biological activity, such as mitomycin, vincamine and the like, and is widely applied in the fields of material chemistry, medicinal chemistry, dyes and the like. Currently, only a few methods for synthesizing [ a ] -annulated indoles are reported, for example, one-pot methods using intramolecular alkyl migration reactions of indole organoboron reagents, as shown in scheme A (Ishikura M, Terashimam. tetrahedron letters,1992,33(45):6849-6852.Ishikura M, Ida W, Yanadak. tetrahedron,2006,62(5): 1015-1024.); the Wittig method is shown in scheme B (Schweizer E E, Light K. the Journal of Organic Chemistry,1966,31(3): 870-872.); free radical cyclization and substitution processes as shown in the scheme C1 (Ziegler F E, Jeroncic L O. the Journal of Organic Chemistry,1991,56(11):3479-3486.Caddick S, Aboutayab K, West R. Synlett,1993 (03):231-232.Caddick S, Aboutayab K, West R I. Journal of the Chemical Society, Chemical Communications,1995(13):1353-1354.) and transition metal catalyzed hydrocarbon activation processes as shown in the schemes C2 and D (arthritis D R, Cho I S, Jaime-Figuero S, et al.1994 Journal of Organic Chemistry, 137, 59(9): 6-2466. Verongic A O, silane-B2811. C. J. Pat. No. 11. Calronycycline A, Kallman J. 3, Oc. J. Et 11. Journal of Chemical Chemistry, Kalll J. 3, Oc. J. 3, Occid. 3-1354. and. C1, bytschkov I, Doye S. Angewandte Chemie International edition,2003,42(26): 3042-3044), and the like. However, these conventional methods for the synthesis of [ a ] -annulated indole compounds generally require pre-activation of the indole substrate and often result in lower yields through a multi-step synthetic route.
Disclosure of Invention
The invention aims to provide a method for synthesizing [ a ] -cyclized indole derivatives, which has the advantages of mild condition, higher yield and environmental protection.
In order to achieve the purpose, the technical scheme of the invention is as follows: a process for the synthesis of a cyclized indole derivative of the general formula (I) [ a ],
is prepared from substituted indoles of general formula (II) and dihaloalkanes of general formula (III)
Under the participation of a palladium catalyst, norbornene, alkali and water, the alkylation of C2 position of substituted indole and the domino reaction of N-H ring closure are realized, and the reaction formula is as follows:
wherein, R group is selected from hydrogen, alkoxy, nitryl, cyano, halogeno, methyl, amino, acyl and the like, and R group is substituted at C3, C4, C5, C6 or C7 position of indole ring;
wherein, X1Selected from bromine, X2Selected from chlorine, bromine;
wherein n is selected from 1,2,3 …
The method comprises the following specific steps:
dissolving substituted indole, dihalogenated alkane, a palladium catalyst, norbornene and alkali in a mixed solvent, uniformly mixing, reacting for 12-36 hours at the reaction temperature of 80 +/-20 ℃, filtering short silica gel after the reaction is finished to remove insoluble impurities, extracting for 3 times by using ethyl acetate and water, extracting for 1 time by using brine, removing the solvent from an organic phase to obtain a crude product, and performing column chromatography separation on the crude product to obtain the target compound.
In one embodiment of the present invention, 1, 3-dibromopropane is used as the dihaloalkane, and the molar amount is 2.5 times that of the substituted indole.
In one embodiment of the invention, the palladium catalyst is bis-acetonitrile palladium dichloride in a molar amount of 0.1 times the molar amount of the substituted indole.
In one embodiment of the present invention, the molar amount of norbornene is 5 times the molar amount of substituted indole.
In one embodiment of the invention, the alkali is cesium carbonate or potassium carbonate, and the molar weight of the alkali is 2-4 times of that of the indole compound.
In one embodiment of the present invention, the solvent is a mixed solvent of DMA or DMF and water, and the concentration of water in the mixed solvent is 0.5M.
Compared with the prior art, the invention has the following remarkable effects:
(1) the widely available and cheap indole is used as a starting material, and the [ a ] -cyclic indole compound is synthesized by one-step series reaction, so that the method is more efficient than the traditional multi-step synthesis method.
(2) The reaction method of hydrocarbon activation is used, so that the pre-activation of the reaction of the conventional synthesis method is avoided, the atom economy is high, and the method is green, simple and convenient.
Detailed Description
The present invention is further illustrated by the following examples.
Experimental example 1
Synthesis of 2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
1H-indole reactant (0.2mmol,23.4mg) was accurately weighed, transferred to a reaction vessel, and 1, 3-dibromopropane (0.5mmol, 50. mu.L), PdCl, added to the reaction vessel2(MeCN)2(10% mmol,5.2mg), norbornene (1.0mmol, 94.2mg), cesium carbonate (0.8mmol,260.7mg), dropwise adding 1ml of DMA and 9. mu.L of water to a thick-walled pressure-resistant tube, sealing the reaction system by screwing a reaction plug, heating to 80 ℃, and reacting for 12 hours under oil bath stirring. After the reaction is finished, cooling the reaction liquid to room temperature, filtering by short silica gel to remove insoluble impurities, extracting for 3 times by using ethyl acetate and water, extracting for 1 time by using brine, removing the solvent by using an organic phase to obtain a crude product, and performing column chromatography separation on the crude product (eluent: ethyl acetate/petroleum ether is 1:50) to obtain a pure and dry product with the yield of 60%.1H NMR (300MHz, CDCl3) δ 7.55(d, J ═ 7.9Hz,1H),7.25(d, J ═ 9.2Hz,1H),7.09(dtd, J ═ 14.6,7.0,1.1Hz,2H),6.17(d, J ═ 0.8Hz,1H), 4.13-4.01 (m,2H),3.03(t, J ═ 7.4Hz,2H),2.61(dd, J ═ 14.2,7.2Hz,2H), the spectra were consistent with the data reported in the literature. (Ishikura M, IdaW, Yanada K. tetrahedron,2006,62(5):1015-1024.)
Experimental example 2
Synthesis of 2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
Accurately weigh the 1H-indole reactant (0.2mmol,23.4mg), transfer to a reaction vessel, add 1-bromo-3-chloropropane (0.5 mmol), PdCl to the reaction vessel2(MeCN)2(10% mmol,4.48mg), norbornene (0.2mmol, 55mg), cesium carbonate (0.8mmol,10.8mg), dropwise adding 1ml of DMA and 9. mu.L of water to a thick-walled pressure-resistant tube, sealing the reaction system by screwing a reaction plug, heating to 80 ℃, and reacting for 12 hours under oil bath stirring. After the reaction is finished, the reaction solution isCooling to room temperature, filtering with short silica gel to remove insoluble impurities, extracting with ethyl acetate and water for 3 times, extracting with brine for 1 time, removing solvent from organic phase to obtain crude product, and performing column chromatography separation on the crude product (eluent: ethyl acetate/petroleum ether: 1:50) to obtain pure dry product with yield of 34%.1HNMR (300MHz, CDCl3) δ 7.55(d, J ═ 7.9Hz,1H),7.25(d, J ═ 9.2Hz,1H),7.09(dtd, J ═ 14.6,7.0,1.1Hz,2H),6.17(d, J ═ 0.8Hz,1H), 4.13-4.01 (m,2H),3.03(t, J ═ 7.4Hz,2H),2.61(dd, J ═ 14.2,7.2Hz,2H), the spectra were consistent with the data reported in the literature. (Ishikura M, Ida W, YanadaK. tetrahedron,2006,62(5):1015-1024.)
Experimental example 3
Synthesis of 2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
1H-indole reactant (0.2mmol,23.4mg) was accurately weighed, transferred to a reaction vessel, and 1, 3-dibromopropane (0.5mmol, 50. mu.L), PdCl, added to the reaction vessel2(MeCN)2(10% mmol,5.2mg), norbornene (1.0mmol, 94.2mg), cesium carbonate (0.8mmol,260.7mg), dropwise adding 1ml of DMMF and 9. mu.L of water into a thick-walled pressure-resistant tube, sealing the reaction system by screwing a reaction plug, heating to 80 ℃, and reacting for 12 hours under oil bath stirring. After the reaction is finished, cooling the reaction liquid to room temperature, filtering the reaction liquid by short silica gel to remove insoluble impurities, extracting the reaction liquid by ethyl acetate and water for 3 times, extracting the reaction liquid by brine for 1 time, removing the solvent by an organic phase to obtain a crude product, and performing column chromatography separation on the crude product (eluent: ethyl acetate/petroleum ether is 1:50) to obtain a pure and dry product with the yield of 49 percent.1H NMR (300MHz, CDCl3) δ 7.55(d, J ═ 7.9Hz,1H),7.25(d, J ═ 9.2Hz,1H),7.09(dtd, J ═ 14.6,7.0,1.1Hz,2H),6.17(d, J ═ 0.8Hz,1H), 4.13-4.01 (m,2H),3.03(t, J ═ 7.4Hz,2H),2.61(dd, J ═ 14.2,7.2Hz,2H), the spectra were consistent with the data reported in the literature. (Ishikura M, IdaW, Yanada K. tetrahedron,2006,62(5):1015-1024.)
Experimental example 4
Synthesis of 5-methoxy-2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
The 5-methoxy-1H-indole reactant (0.2mmol,29.4mg) was accurately weighed, transferred to a reaction vessel, and 1, 3-dibromopropane (0.5mmol, 50. mu.L), PdCl, added to the reaction vessel2(MeCN)2(10% mmol,5.2mg) norBornylene (1.0mmol, 94.2mg), cesium carbonate (0.8mmol,260.7mg), 1ml of DMA and 9. mu.L of water were added dropwise to a thick-walled pressure-resistant tube, a reaction plug was screwed to seal the reaction system, the temperature was heated to 80 ℃, and the reaction was carried out for 12 hours under stirring in an oil bath. After the reaction is finished, the reaction liquid is cooled to room temperature, the short silica gel is filtered to remove insoluble impurities, ethyl acetate and water are used for extraction for 3 times, brine is used for extraction for 1 time, the organic phase is used for removing the solvent to obtain a crude product, and the crude product is subjected to column chromatography separation (eluent: ethyl acetate/petroleum ether is 1:50) to obtain a pure and dry product, wherein the yield is 57%.1H NMR (300MHz, CDCl3) δ 7.13(d, J ═ 8.8Hz,1H),7.04(d, J ═ 2.2Hz,1H),6.78(dd, J ═ 8.7,2.3Hz,1H),6.09(s,1H),4.03(t, J ═ 6.9Hz,2H),3.85(s,3H),3.01(t, J ═ 7.3Hz,2H), 2.67-2.54 (m,2H) the spectrum is consistent with literature reported data. (Ishikura M, Ida W, Yanada K. tetrahedron,2006,62(5):1015-1024.)
Experimental example 5
Synthesis of 6-chloro-2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
6-chloro-1H-indole reactant (0.2mmol,30.3mg) was accurately weighed, transferred to a reaction vessel, and 1, 3-dibromopropane (0.5mmol, 50. mu.L), PdCl, was added to the reaction vessel2(MeCN)2(10% mmol,5.2mg), norbornene (1.0mmol, 94.2mg), cesium carbonate (0.4mmol,130.3mg), dropwise adding 1ml of DMA and 9. mu.L of water into a thick-walled pressure-resistant tube, sealing the reaction system by screwing a reaction plug, heating to 80 ℃, and reacting for 24 hours under oil bath stirring. After the reaction, the reaction solution was cooled to room temperature, the insoluble impurities were removed by filtration over short silica gel, extracted 3 times with ethyl acetate and water, extracted 1 time with brine, the solvent was removed from the organic phase to give a crude product, which was subjected to column chromatography (eluent: ethyl acetate/petroleum ether: 1:50) to give pure dry product with a yield of 47%.1H NMR(300MHz,CDCl3)δ7.43(d,J＝8.4Hz,1H),7.22(s,1H),7.02(dd,J＝8.4,1.8Hz,1H),6.13(s,1H),4.01(d,J＝6.9Hz,2H),3.00(d,J＝7.7Hz,2H),2.64–2.58(m,2H).13C NMR(75MHz,CDCl3)δ145.37,132.94,131.74,125.85,120.95,119.57,109.33,92.53,43.54,27.68,24.15.
Experimental example 6
Synthesis of 5-iodo-2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
The 5-iodo-1H-indole reactant (0.2mmol,48.6mg) was accurately weighed, transferred to a reaction vessel, and 1, 3-dibromopropane (0.5mmol, 50. mu.L), PdCl, was added to the reaction vessel2(MeCN)2(10% mmol,5.2mg), norbornene (1.0mmol, 94.2mg), cesium carbonate (0.4mmol,130.3mg), dropwise adding 1ml of DMA and 9. mu.L of water into a thick-walled pressure-resistant tube, sealing the reaction system by screwing a reaction plug, heating to 80 ℃, and reacting for 12 hours under oil bath stirring. After the reaction is finished, the reaction liquid is cooled to room temperature, the short silica gel is filtered to remove insoluble impurities, ethyl acetate and water are used for extraction for 3 times, brine is used for extraction for 1 time, the organic phase is used for removing the solvent to obtain a crude product, and the crude product is subjected to column chromatography separation (eluent: ethyl acetate/petroleum ether is 1:50) to obtain a pure and dry product, wherein the yield is 52%.1H NMR(300MHz,CDCl3)δ7.66(d,J＝1.6Hz,1H),7.19(dd,J＝8.5,1.8Hz,1H),7.09(d,J＝8.5Hz,1H),6.11(d,J＝0.6Hz,1H),4.03(t,J＝7.0Hz,2H),3.02(t,J＝7.5Hz,2H),2.66–2.57(m,2H).13C NMR(75MHz,CDCl3)δ145.89,134.81,131.26,122.74,122.60,112.29,110.61,92.05,43.70,27.69,24.29.
Experimental example 7
Synthesis of 2-nitro-6, 7,8, 9-tetrahydropyrido [1,2- α ] indole
The 5 nitro-1H-indole reactant (0.2mmol,32.4mg) was accurately weighed, transferred to a reaction vessel, and 1, 4-dibromobutane (0.5mmol, 60. mu.L), PdCl, added to the reaction vessel2(MeCN)2(10% mmol,5.2mg), norbornene (1.0mmol, 94.2mg), potassium carbonate (0.8mmol,110.6mg), dropwise adding 1ml of DMA and 9. mu.L of water into a thick-walled pressure-resistant tube, screwing a reaction tube plug to seal the reaction system, heating to 80 ℃, and reacting for 36 hours under oil bath stirring conditions. After the reaction is finished, cooling the reaction liquid to room temperature, filtering by short silica gel to remove insoluble impurities, extracting for 3 times by using ethyl acetate and water, extracting for 1 time by using brine, removing the solvent by using an organic phase to obtain a crude product, and performing column chromatography separation on the crude product (eluent: ethyl acetate/petroleum ether is 1:50) to obtain a pure and dry product with the yield of 30%. 1H NMR (500MHz, CDCl3) δ 8.46(d, J ═ 2.1Hz,1H),8.04(dd, J ═ 8.9,2.2Hz,1H),7.24(s,1H),6.36(s,1H),4.10(t, J ═ 6.2Hz,2H),3.01(t, J ═ 6.3Hz,2H), 2.14-2.09 (m,2H), 1.94-1.90 (m,2H).
Experimental example 8
Synthesis of 5-cyano-2, 3-dihydro-1H-pyrrolo [1,2-a ] indole
The 5-cyano-1H-indole reactant (0.2mmol,36.4mg) was accurately weighed, transferred to a reaction vessel, and 1, 3-dibromopropane (0.5mmol, 50. mu.L), PdCl, was added to the reaction vessel2(MeCN)2(10% mmol,5.2mg), norbornene (1.0mmol, 94.2mg), potassium carbonate (0.8mmol,110.6mg), dropwise adding 1ml of DMA and 9. mu.L of water into a thick-walled pressure-resistant tube, screwing a reaction tube plug to seal the reaction system, heating to 80 ℃, and reacting for 24 hours under oil bath stirring. After the reaction, the reaction solution was cooled to room temperature, the insoluble impurities were removed by filtration over short silica gel, extracted 3 times with ethyl acetate and water, extracted 1 time with brine, the solvent was removed from the organic phase to give a crude product, which was subjected to column chromatography (eluent: ethyl acetate/petroleum ether: 1:50) to give pure dry product with a yield of 47%.1H NMR(500MHz,CDCl3)δ7.84(s,1H),7.32(ddd,J＝8.4,2.3,1.3Hz,1H),7.23(dd,J＝8.4,2.1Hz,1H),6.22(s,1H),4.09(td,J＝7.0,2.2Hz,2H),3.04(dd,J＝7.8,7.1Hz,2H),2.68–2.61(m,2H).13C NMR(126MHz,CDCl3)δ147.25,134.23,132.94,125.59,123.28,121.29,110.14,101.83,93.63,77.44,77.19,76.94,43.89,27.84,24.31.。
Claims (10)
1. A process for the synthesis of a cyclic indole derivative of general formula (I) [ a ],
I
is prepared from substituted indole of general formula (II) and dihaloalkane of general formula (III)
II III
Under the participation of palladium catalyst, norbornene, alkali and water, the alkylation of C2 site of substituted indole and the domino reaction of N-H ring closure are realized,
wherein, R group is selected from hydrogen, alkoxy, nitryl, cyano, halogeno, methyl, amino or acyl, and R group is substituted at C3, C4, C5, C6 or C7 position of indole ring;
X1selected from bromine, X2Selected from chlorine, bromine;
n is selected from 1,2 and 3.
2. The method of claim 1, wherein the R group is selected from the group consisting of hydrogen, alkoxy, nitro, cyano, and halo.
3. The method of synthesis of claim 1, wherein n is selected from 1 or 2.
4. The method of claim 1 wherein the dihaloalkane is 1, 3-dibromopropane present in a molar amount of 2.5 times the molar amount of the substituted indole.
5. The synthesis method of claim 1, wherein the palladium catalyst is bis-acetonitrile palladium dichloride in a molar amount of 0.1 times that of the substituted indole.
6. The synthesis process of claim 1, wherein the base is cesium carbonate or potassium carbonate in a molar amount of 2-4 times that of the indole compound.
7. The method of claim 1 wherein the norbornene is present in a molar amount 5 times the molar amount of the substituted indole.
8. The method of claim 1, wherein the solvent is a mixture of DMA or DMF and water, and the concentration of water in the mixture is 0.5M.
9. The synthesis process according to claim 1, characterized in that the reaction temperature is 60-100 ℃.
10. The method of synthesis according to claim 1, wherein the reaction time is 12 to 36 hours.
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| WO1992016529A1 (en) * | 1991-03-25 | 1992-10-01 | Boehringer Mannheim Gmbh | Novel isoindole derivatives and medicaments containing them |
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| WO1992016529A1 (en) * | 1991-03-25 | 1992-10-01 | Boehringer Mannheim Gmbh | Novel isoindole derivatives and medicaments containing them |
Non-Patent Citations (3)
| Title |
|---|
| Indole Functionalization via Photoredox Gold Catalysis;Sherif J. Kaldas 等;《Org. Lett.》;20150522;第17卷(第11期);第2864-2866页 * |
| Oxidative Radical Cyclization of (ω-Iodoalkyl)indoles and Pyrroles. Synthesis of (-)-Monomorine and Three Diastereomers;Dean R. Artis 等;《J. Org. Chem.》;19941231;第59卷(第9期);第2456-2466页 * |
| Palladium-Catalyzed, Ring-Forming Aromatic C−H Alkylations with Unactivated Alkyl Halides;Alexander R. O. Venning 等;《J. Am. Chem. Soc.》;20150306;第137卷(第11期);第3731-3734页 * |
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