CN114890932A - First total synthesis process of indole alkaloid Luteoride A - Google Patents
First total synthesis process of indole alkaloid Luteoride A Download PDFInfo
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- CN114890932A CN114890932A CN202210729385.XA CN202210729385A CN114890932A CN 114890932 A CN114890932 A CN 114890932A CN 202210729385 A CN202210729385 A CN 202210729385A CN 114890932 A CN114890932 A CN 114890932A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D209/22—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 with an aralkyl radical attached to the ring nitrogen atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a first total synthesis process of indole alkaloid Luteoride A in the Luteoride A synthesis field, wherein an isoprene group is introduced into the 7 th site of indole, so that the use of toxic reagents (trimethyl silanization diazomethane, cuprous cyanide, 2-methyl-1-butene-3-alkyne and the like), highly flammable reagents (n-butyllithium, tri-n-butyltin hydride and the like) and expensive reagents (trimethyl silanization diazomethane, child naphthol borane, 2-methyl-1-butene-3-alkyne and the like) is avoided, and the operation without a protective group is also used, so that the process has redox economy and atomic economy; and realizes the first total synthesis of indole alkaloid luteorideA.
Description
Technical Field
The invention relates to the technical field of LuteorideA synthesis, in particular to a first total synthesis process of indole alkaloid LuteorideA.
Background
At present, no precedent for directly introducing an isoprene group at the 7-position of indole under the operation without a protecting group exists, and the traditional method has certain limitation in the process of introducing the isoprene group, and generally needs harsh reaction conditions such as strong acid and strong base, highly toxic reagents (trimethylsilylated diazomethane, cuprous cyanide, 2-methyl-1-butene-3-alkyne and the like), highly flammable reagents (n-butyllithium, tri-n-butyltin hydride, catechol borane and the like) and expensive reagents (trimethylsilylated diazomethane, naphthol borane, 2-methyl-1-butene-3-alkyne and the like). Atom economy is poor, preparation cost is high, total yield is low, and no relevant report on the synthesis of indole alkaloid luteorideA exists at present.
Based on the technical scheme, the invention designs a first total synthesis process of indole alkaloid LuteorideA to solve the problems.
Disclosure of Invention
The invention aims to provide a first total synthesis process of indole alkaloid Luteoridea A, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the primary total synthesis process of indole alkaloid LuteorideA comprises the following steps:
s1: a substrate 4 is taken as a starting material and undergoes a hydroxylamination reaction with hydroxylamine hydrochloride to obtain a compound 5 with a yield of 87%; the method specifically comprises the following steps: 335mL CHC13, and 221mL CH3OH were added to a dry reaction flask under nitrogen, 417.7mL (165.8mmol) of substrate was added at room temperature, stirring was uniform, and 10.7g HCl-amine (165.8mmol) was added; the mixture was stirred overnight at room temperature and then concentrated by rotary evaporation at 30 ℃ to remove most of the solvent, with little solvent remaining; the residue was dissolved in 300mL of dichloromethane, washed successively with 0.1N of 30mL HC1, 230mL of water, and 30mL of saturated sodium chloride solution, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated to give 28.3g of Compound 5 as white crystals (87% yield); no further purification was required.
S2, adding excess initial raw material 2-methyl-1-butene-3-alkyne 1 into naphthol borane to obtain a compound 2;
the compound 3 is obtained by adding cuprous cyanide, flammable compounds n-butyl lithium and tri-n-butyl tin hydride into 2-methyl-1-butene-3-alkyne 1.
Preparation of prenyl Compounds
The compound 5 and a 7-bromoindole substrate 6 undergo a heteroatom D-A reaction and then undergo ring opening and aromatization to obtain a compound 7 with a yield of 82%, specifically: under nitrogen protection, 10g of compound 2(51mmol) was dissolved in 110mL of dichloromethane and added dropwise to 20g of 7-bromoindole 3(102mmol) dissolved in 110mL of dichloromethane and treated with 10.8g of Na2CO3(102mmol), the mixture was stirred at room temperature for 10h and then extracted with 200mL of dichloromethane, washed successively with 220mL of water and 20mL of saturated sodium chloride solution, the organic phases were combined and dried over anhydrous sodium sulfate, filtered and the solvent was removed by rotary evaporation at 30 ℃ to give compound 2, and the residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetate ═ 5:1 to 3:1) to give 13g of compound 4 (yield 82%).
S3: the compound 7 and 2-methyl-3-butene-2-ol 8 are subjected to Heck reaction in the presence of a palladium catalyst, and the tertiary hydroxyl is eliminated in situ to obtain LuteorideA with a yield of 94%; the method specifically comprises the following steps: under nitrogen protection, 1.12g of compound 4(3.6mol), 64.8mg of catalyst (0.288mmo1), 219.6mg of tris (o-methylphenyl) phosphine (0.72mmol), 79.2mg of BHT (0.36mmol), DMF 19.2mL, 772 μ L N-methyldicyclohexylamine (3.6mmol) and 1.7mL of 2-methyl-3-buten-2-ol 5(54mmol) are put into a sealed tube in succession, mixed uniformly and reacted in an oil bath at 115 ℃ for 6 hours, after cooling, stirred with 10mL of sodium bicarbonate solution for 5 minutes, the insoluble matter is filtered through silica gel and the filter cake is washed with 150mL of ethyl acetate, the filtrate is washed once with (5X 30mL) of water and 30mL of saturated sodium chloride solution, the organic phases are combined and dried over anhydrous sodium sulfate, filtered and then concentrated at 30 ℃ by rotary evaporation to remove the solvent; the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate: 5:1-1:1) to give 978mg of Luteoride A (yield 92%).
As a further scheme of the invention, in the first step, the substrate 4 is methyl bromopyruvate, ethyl bromopyruvate, methyl chlorophytonate, ethyl chlorophytonate, propyl chlorophytonate, methyl iodopyruvate, ethyl iodopyruvate or propyl iodopyruvate.
As a further embodiment of the invention, the catalyst in the third step is palladium acetate, palladium chloride, tetratriphenylphosphine palladium, tris (diylideneacetone) dipalladium-chloroform adduct, tris (diylideneacetone) dipalladium, palladium trifluoroacetate, bis (tri-tert-butylphosphine) palladium, palladium on carbon or no catalyst is added.
As a further embodiment of the present invention, in the second step, the substrate 6 is 7-bromoindole, 4-bromoindole, 5-bromoindole or 6-bromoindole.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, an isoprene group is introduced into the 7 th position of indole for the first time, so that the use of toxic reagents (trimethylsilylated diazomethane, cuprous cyanide, 2-methyl-1-butene-3-alkyne and the like), highly flammable reagents (n-butyllithium, tri-n-butyltin hydride and the like) and expensive reagents (trimethylsilylated diazomethane, naphthol borane, 2-methyl-1-butene-3-alkyne and the like) is avoided, and the use of a protecting group-free operation is adopted, so that the preparation method has redox economy and atomic economy; and realizes the first total synthesis of indole alkaloid luteorideA; generally, the synthesis method has the advantages of simple and direct route, simple and easily obtained raw materials, low preparation cost, high product yield, simple and convenient operation and the like.
Drawings
FIG. 1 is a schematic nuclear magnetic resonance hydrogen spectrum of a substrate 5 of the present invention;
FIG. 2 is a schematic nuclear magnetic resonance carbon spectrum of a substrate 5 of the present invention;
FIG. 3 is a schematic nuclear magnetic resonance hydrogen spectrum of a substrate 7 of the present invention;
FIG. 4 is a schematic nuclear magnetic resonance carbon spectrum of a substrate 7 of the present invention;
FIG. 5 is a schematic illustration of the hydrogen nuclear magnetic resonance spectrum of LuteorideA according to the present invention;
FIG. 6 is a schematic nuclear magnetic resonance carbon spectrum of LuteorideA according to the present invention.
Detailed Description
Referring to fig. 1-6, the present invention provides a technical solution: the first total synthesis process of the indole alkaloid Luteoridea A comprises the following steps:
s1: a substrate 4 is taken as a starting material and undergoes a hydroxylamination reaction with hydroxylamine hydrochloride to obtain a compound 5 with a yield of 87%; the method specifically comprises the following steps: 335mL of CHC13 and 221mLCH3OH were added to a dry reaction flask under nitrogen, 417.7mL (165.8mmol) of substrate was added at room temperature, the mixture was stirred well, and then 10.7g of hydrochloric acid and amine (165.8mmol) were added; the mixture was stirred overnight at room temperature and then concentrated by rotary evaporation at 30 ℃ to remove most of the solvent, with little solvent remaining; the residue was dissolved in 300mL of dichloromethane, washed successively with 0.1N of 30mL HC1, 230mL of water, and 30mL of saturated sodium chloride solution, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated to give 28.3g of Compound 5 as white crystals (87% yield); no further purification was required.
White solid, total yield 87%, 1 H NMR(400MHz,Acetone-d 6 )δ4.39(d,2H),3.82(s,3H)； 13 C NMR(101MHz,Acetone-d 6 )δ162.73,147.57,51.92,15.97.
s2, adding excess initial raw material 2-methyl-1-butene-3-alkyne 1 into naphthol borane to obtain a compound 2;
and then adding a compound cuprous cyanide, a flammable compound n-butyl lithium and tri-n-butyl tin hydride into the 2-methyl-1-butene-3-alkyne 1 to obtain a compound 3.
Preparation of prenyl Compounds
The compound 5 and a 7-bromoindole substrate 6 undergo a heteroatom D-A reaction and then undergo ring opening and aromatization to obtain a compound 7 with a yield of 82%, specifically: under nitrogen protection, 10g of compound 2(51mmol) was dissolved in 110mL of dichloromethane and added dropwise to 20g of 7-bromoindole 3(102mmol) dissolved in 110mL of dichloromethane and treated with 10.8g of Na2CO3(102mmol), the mixture was stirred at room temperature for 10h and then extracted with 200mL of dichloromethane, washed successively with 220mL of water and 20mL of saturated sodium chloride solution, the organic phases were combined and dried over anhydrous sodium sulfate, filtered and the solvent was removed by rotary evaporation at 30 ℃ to give compound 2, and the residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetate ═ 5:1 to 3:1) to give 13g of compound 4 (yield 82%).
The solid content, the total yield is 82 percent, 1 H NMR(400MHz,CDCl 3 )δ9.47(s,1H),8.22(s,1H),7.72(dt,J＝7.9,0.8Hz,1H),7.34(dd,J＝7.7,0.8Hz,1H),7.21(d,J＝2.4Hz,1H),7.01(t,J＝7.8Hz,1H),4.09(d,J＝0.9Hz,2H),3.82(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ163.78,151.23,134.55,128.39,124.42,124.17,120.77,118.54,110.77,104.67,52.81,20.45.
s3: the compound 7 and 2-methyl-3-butene-2-ol 8 are subjected to Heck reaction in the presence of a palladium catalyst, and the tertiary hydroxyl is eliminated in situ to obtain LuteorideA with a yield of 94%; the method comprises the following specific steps: under nitrogen protection, 1.12g of compound 4(3.6mol), 64.8mg of catalyst (0.288mmo1), 219.6mg of tris (o-methylphenyl) phosphine (0.72mmol), 79.2mg of BHT (0.36mmol), DMF 19.2mL, 772 μ L N-methyldicyclohexylamine (3.6mmol) and 1.7mL of 2-methyl-3-buten-2-ol 5(54mmol) are put into a sealed tube in succession, mixed uniformly and reacted in an oil bath at 115 ℃ for 6 hours, after cooling, stirred with 10mL of sodium bicarbonate solution for 5 minutes, the insoluble matter is filtered through silica gel and the filter cake is washed with 150mL of ethyl acetate, the filtrate is washed once with (5X 30mL) of water and 30mL of saturated sodium chloride solution, the organic phases are combined and dried over anhydrous sodium sulfate, filtered and then concentrated at 30 ℃ by rotary evaporation to remove the solvent; the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate ═ 5:1-1:1) to give 978mg of Luteoride A (92% yield).
The solid content, the total yield is 92 percent, 1 H NMR(400MHz,Acetone-d6)δ11.48(s,1H),10.44(s,1H),7.66(d,J＝7.9Hz,1H),7.37(d,J＝7.4Hz,1H),7.19(d,J＝2.3Hz,1H),7.07(d,J＝4.0Hz,2H),7.03(d,J＝7.7Hz,1H),5.15(d,J＝2.3Hz,1H),5.06(dt,J＝2.9,1.4Hz,1H),4.06(s,2H),3.70(s,3H)； 13 C NMR(101MHz,Acetone-d 6 )δ164.40,151.07,142.58,134.45,131.54,128.19,124.55,123.88,121.24,119.19,118.50,118.36,116.37,109.74,51.43,19.98,17.88；IR(KBr):3332,3050,2944,2346,1705,1438,1340,1206,1106,1013,894,799,728,670,466cm -1 ；HRMS(ESI)m/z calcd for C 17 H 17 N 2 O 3 [M-H] + 297.1246,found297.1245.
as a further scheme of the invention, in the first step, the substrate 4 is methyl bromopyruvate, ethyl bromopyruvate, methyl chlorophytonate, ethyl chlorophytonate, propyl chlorophytonate, methyl iodopyruvate, ethyl iodopyruvate or propyl iodopyruvate.
As a further embodiment of the invention, the catalyst in the third step is palladium acetate, palladium chloride, tetratriphenylphosphine palladium, tris (diylideneacetone) dipalladium-chloroform adduct, tris (diylideneacetone) dipalladium, palladium trifluoroacetate, bis (tri-tert-butylphosphine) palladium, palladium on carbon or no catalyst is added.
As a further embodiment of the present invention, in the second step, the substrate 6 is 7-bromoindole, 4-bromoindole, 5-bromoindole or 6-bromoindole.
Claims (4)
1. A primary total synthesis process of indole alkaloid Luteoride A is characterized in that: the primary total synthesis process of the indole alkaloid Luteoride A comprises the following steps:
s1: a substrate 4 is taken as a starting material and undergoes a hydroxylamination reaction with hydroxylamine hydrochloride to obtain a compound 5 with a yield of 87%; the method specifically comprises the following steps: 335mL of CHC13 and 221mLCH3OH were added to a dry reaction flask under nitrogen, 417.7mL (165.8mmol) of substrate was added at room temperature, the mixture was stirred well, and then 10.7g of hydrochloric acid and amine (165.8mmol) were added; the mixture was stirred overnight at room temperature and then concentrated by rotary evaporation at 30 ℃ to remove most of the solvent, with little solvent remaining; the residue was dissolved in 300mL of dichloromethane, washed successively with 0.1N of 30mL HC1, 230mL of water, and 30mL of saturated sodium chloride solution, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated to give 28.3g of Compound 5 as white crystals (87% yield); no further purification was required.
S2, adding excess initial raw material 2-methyl-1-butene-3-alkyne 1 into naphthol borane to obtain a compound 2;
and then adding a compound cuprous cyanide, a flammable compound n-butyl lithium and tri-n-butyl tin hydride into the 2-methyl-1-butene-3-alkyne 1 to obtain a compound 3.
Preparation of prenyl Compounds
The compound 5 and a 7-bromoindole substrate 6 undergo a heteroatom D-A reaction and then undergo ring opening and aromatization to obtain a compound 7 with a yield of 82%, specifically: under nitrogen protection, 10g of compound 2(51mmol) was dissolved in 110mL of dichloromethane and added dropwise to 20g of 7-bromoindole 3(102mmol) dissolved in 110mL of dichloromethane and treated with 10.8g of Na2CO3(102mmol), the mixture was stirred at room temperature for 10h and then extracted with 200mL of dichloromethane, washed successively with 220mL of water and 20mL of saturated sodium chloride solution, the organic phases were combined and dried over anhydrous sodium sulfate, filtered and the solvent was removed by rotary evaporation at 30 ℃ to give compound 2, and the residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetate ═ 5:1 to 3:1) to give 13g of compound 4 (yield 82%).
S3: the compound 7 and 2-methyl-3-butene-2-ol 8 are subjected to Heck reaction in the presence of a palladium catalyst, and the tertiary hydroxyl is eliminated in situ to obtain Luteoride A with a yield of 94%; the method specifically comprises the following steps: under nitrogen protection, 1.12g of compound 4(3.6mol), 64.8mg of catalyst (0.288mmo1), 219.6mg of tris (o-methylphenyl) phosphine (0.72mmol), 79.2mg of BHT (0.36mmol), DMF 19.2mL, 772 μ L N-methyldicyclohexylamine (3.6mmol) and 1.7mL of 2-methyl-3-buten-2-ol 5(54mmol) are put into a sealed tube in succession, mixed uniformly and reacted in an oil bath at 115 ℃ for 6 hours, after cooling, stirred with 10mL of saturated sodium bicarbonate solution for 5 minutes, the insoluble matter is filtered through silica gel and the filter cake is washed with 150mL of ethyl acetate, the filtrate is washed once with (5 × 30mL) of water and 30mL of saturated sodium chloride solution, the organic phases are combined and dried over anhydrous sodium sulfate, filtered and then concentrated by rotary evaporation at 30 ℃ to remove the solvent; the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate ═ 5:1-1:1) to give 978mg of Luteoride A (92% yield).
2. The process for the first total synthesis of indole alkaloid Luteoride A according to claim 1, wherein: in the first step, the substrate 4 is methyl bromopyruvate, ethyl bromopyruvate, methyl chlorophyruvate, ethyl chlorophyruvate, propyl chlorophyruvate, methyl iodopyruvate, ethyl iodopyruvate or propyl iodopyruvate.
3. The process for the first total synthesis of indole alkaloid Luteoride A according to claim 1, wherein: the catalyst in the third step is palladium acetate, palladium chloride, tetratriphenylphosphine palladium, a tri (diylideneacetone) dipalladium-chloroform adduct, tri (diylideneacetone) dipalladium, palladium trifluoroacetate, di (tri-tert-butylphosphine) palladium, palladium carbon or no catalyst is added.
4. The process for the first total synthesis of indole alkaloid Luteoride A according to claim 1, wherein: in the second step, the substrate 6 is 7-bromoindole, 4-bromoindole, 5-bromoindole or 6-bromoindole.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101720315A (en) * | 2007-02-28 | 2010-06-02 | 法国国家科学研究中心 | Novel derivatives of psammaplin a, a method for their synthesis and their use for the prevention or treatment of cancer |
| CN114539123A (en) * | 2022-02-28 | 2022-05-27 | 大理大学 | Method for synthesizing TMC-205 in one step |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101720315A (en) * | 2007-02-28 | 2010-06-02 | 法国国家科学研究中心 | Novel derivatives of psammaplin a, a method for their synthesis and their use for the prevention or treatment of cancer |
| CN114539123A (en) * | 2022-02-28 | 2022-05-27 | 大理大学 | Method for synthesizing TMC-205 in one step |
Non-Patent Citations (2)
| Title |
|---|
| MASAHIKO ISAKA等: ""Conoideoxime A, antibacterial bis-oxime prenyl-tryptophan dimer from the whitefly pathogenic fungus Conoideocrella luteorostrata BCC 76664"" * |
| RAQUEL PEREIRA等: ""Indole-Derived Psammaplin A Analogues as Epigenetic Modulators with Multiple Inhibitory Activities"" * |
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