CN112409344B - Synthesis method of natural product Scleropentadide A - Google Patents

Synthesis method of natural product Scleropentadide A Download PDF

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CN112409344B
CN112409344B CN202011002811.7A CN202011002811A CN112409344B CN 112409344 B CN112409344 B CN 112409344B CN 202011002811 A CN202011002811 A CN 202011002811A CN 112409344 B CN112409344 B CN 112409344B
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scleropentadide
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胡祥国
卢继亮
潘强
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Jiangxi Normal University
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    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention discloses a method for synthesizing a natural product Scleropentadide A, which comprises the following steps: 1) carrying out esterification reaction on the glycosyl acid compound and thiophenol to obtain a thiosugar acid ester compound; 2) carrying out coupling-desulfurization reaction on the thiosugar acid ester compound and 2-furanboronic acid to obtain a glycosyl furanone compound; 3) the glycosyl furanone compound and methanol are subjected to carbonyl protection reaction to obtain a ketal compound; 4) and carrying out deprotection reaction on the ketal compound to obtain the ketal compound. Compared with the existing synthesis method, the method has the advantages that the yield is greatly improved, the total yield reaches more than 69%, the yield of gram level can be realized, and the adopted reagent is safe for human bodies.

Description

Synthesis method of natural product Scleropentaside A
Technical Field
The invention relates to a synthetic method of a natural medicine, in particular to an artificial synthetic method of natural Scleropentadide A, and belongs to the technical field of medicine synthesis.
Background
Scleropentadines are a very classical group of natural products which are found extensively in the rhizomes and leaves of the plants Scleropyrum pentadram and Dendrotrophe frutescens, which plants can be used in Asian traditional medicine for contraception, treatment of rheumatic diseases and skin diseases, etc. Thus, Scleropentadias is a natural product with very excellent medical value. Furthermore, Scleropentadias also have a different expression in chemical structure from other natural sugar compounds, and in many natural product sugar compounds, the C-glycoside configuration at the anomeric position generally exhibits an α configuration, while the anomeric position on the sugar ring of the Scleropentadias exhibits a β configuration. In 2012, Tripetch Kanchanapom, Wannaporn Scalepentaside et al performed detailed structural characterization of Scleropentadines in Undrected furan-2-carbonyl C-glycosides and phenolic di-saccharides from Scleropyrum montanum, published in the journal "Phytochemistry". In 2018, Maciej A. Walczak, Feng Zhu, Jacob Rodriguez and Sloane O' Neill in published article Acyl carbohydrates through step glucose Cross-Coupling: Rapid Access to C (sp3) Linked carbohydrates mentioned the synthesis of the natural product Scleropentadiade A, as shown in FIG. 1, the all benzyl protected Scleropentadiade A was synthesized with a yield of only 40%.
Figure BDA0002694911630000011
In 2019, the complete Synthesis scheme of the natural product Screopentaside A was reported in the publication by G.Jacob Boehlich and Nina Schgtzenmeister in the Synthesis of Screopentaside A:
Figure BDA0002694911630000021
as shown in FIG. 2, the synthesis of the natural product, Scleropentadide A, from the initial substrate to the final substrate takes 4-5 steps, and the total yield is only 47%.
Therefore, the invention of the efficient and simple synthesis square normal line of the natural product Scleropentadide A is particularly necessary.
Disclosure of Invention
Aiming at the defects of lower yield and the like of a synthetic method of a natural product Scleropentadide A in the prior art, the invention aims to provide the synthetic method of the natural product Scleropentadide A by taking sugar-based acid as a substrate, compared with the existing synthetic method, the yield is greatly improved, the total yield reaches over 69 percent, the yield of gram level can be achieved, and the adopted reagent is safe for human bodies.
In order to achieve the technical purpose, the invention provides a method for synthesizing a natural product Scleropentadide A, which comprises the following steps:
1) carrying out esterification reaction on the glycosyl acid compound and thiophenol to obtain a thiosugar acid ester compound;
2) carrying out coupling-desulfurization reaction on the thiosugar acid ester compound and 2-furanboronic acid to obtain a glycosyl furanone compound;
3) the glycosyl furanone compound and methanol are subjected to carbonyl protection reaction to obtain a ketal compound;
4) carrying out deprotection reaction on the ketal compound to obtain the ketal compound;
the sugar-based acid compound has the structure of formula 1:
Figure BDA0002694911630000022
the thionate compound has a structure of formula 2:
Figure BDA0002694911630000023
Figure BDA0002694911630000031
the glycosyl furanone compound has the structure of formula 3:
Figure BDA0002694911630000032
the glycosyl furanone compound has the structure of formula 4:
Figure BDA0002694911630000033
as a preferred technical scheme, the glycosyl acid compound and the thiophenol are subjected to esterification reaction under the action of a HATU condensation reagent, a DIPEA coupling reagent and an organic base to obtain the thiosugar acid ester compound. The esterification reaction employs methylene chloride as a benign reaction solvent. During the esterification reaction, the sugar-based acid, EDCI, HATU and DIPEA are stirred for 15 minutes at 0 ℃, and after full mixing, the thiophenol is added for reaction.
As a more preferable technical scheme, the molar ratio of the glycosyl acid compound to the organic base is 1: 2-2.3, wherein the organic base is DIPEA.
As a more preferable technical scheme, the molar ratio of the glycosyl acid compound to the HATU condensation reagent and the DIPEA coupling reagent is 1: 4-4.2.
As a more preferable technical scheme, the esterification reaction conditions are as follows: reacting for 6-10 hours at room temperature.
Under the preferable reaction condition of the invention, the yield of the thiosugar acid ester compound obtained by the esterification reaction of the glycosyl acid compound and the thiophenol reaches over 96 percent.
As a preferred technical scheme, the thionate compound and 2-furanboronic acid are reacted in CuTC and Pd2(dba)3Catalyst and P (OEt)3Coupling-desulfurizing reaction is carried out under the action of a desulfurizing agent to obtain the glycosyl furanone compound. The coupling-desulfurization reaction employs tetrahydrofuran as a reaction solvent.
As a more preferable technical scheme, the molar ratio of the thiosugar acid ester compound to the 2-furanboronic acid is 0.16: 0.27-0.3.
As a more preferable technical scheme, the thiosugar acid ester compound, CuTC catalyst and Pd2(dba)3The molar ratio of the catalyst is 0.16: 0.27-0.3: 0.003-0.0035.
As a more preferable technical proposal, the thionate compound and P (OEt)3The molar ratio of the desulfurizing agent is 0.16: 0.03-0.035.
As a more preferred technical scheme, the coupling-desulfurization reaction conditions are as follows: and reacting for 6-16 hours at room temperature under the protection of nitrogen.
Under the preferable reaction condition of the invention, the coupling-desulfurization reaction is carried out on the thiosugar acid ester compound and the 2-furanboronic acid, and the yield of the glycosyl furanone compound is over 96 percent.
As a preferable technical scheme, the glycosyl furanone compound and methanol are subjected to condensation reaction under the catalysis of a dehydrating agent and an inorganic acid to obtain the ketal compound. The mineral acid is preferably sulfuric acid, which is added in catalytic amounts. Methanol is used as a carbonyl protection reagent and a solvent simultaneously in the condensation reaction process, and the addition amount of the methanol is greatly excessive relative to the glycosyl furanone compound. The methyl alcohol adopted by the invention is taken as a protective group, is common and easy to obtain, has small molecular weight, is easy to operate, and is matched with a dehydrating agent trimethyl orthoformate.
As a more preferable technical scheme, the molar ratio of the glycosyl furanone compound to the dehydrating agent is 1: 20-21; the dehydrating agent is trimethoxy methane.
As a more preferred technical solution, the condensation reaction conditions are: and reacting for 6-10 hours at room temperature.
The ketal compounds obtained by the condensation reaction of the invention are relatively unstable and are easily decomposed back to glycosyl furanones, so the ketal compounds need to be quickly used for the next deprotection reaction.
As a preferable technical scheme, the ketal compound and sodium methoxide are subjected to deprotection reaction under an acidic condition to obtain Scleropentadide A. During the deprotection reaction, the protecting group is removed, and meanwhile pivaloyl is removed (Piv).
As a more preferable technical scheme, the molar ratio of the ketal compound to the MeONa is 0.84: 0.25-0.27;
preferably, the acidic condition is a pH of 1.8 to 2.2, and the acidic condition is adjusted by using an acidic resin. The acidic resin is specifically a sodium type cation exchange resin.
As a preferred technical scheme, the conditions of the deprotection reaction are as follows: and reacting at room temperature for 3-5 hours.
Under the preferable conditions of the invention, the yield of the glycosyl furanone compound converted into the Scleropentadide A can be improved to over 75 percent by protecting the carbonyl group by methoxy and then hydrolyzing to remove pivaloyl.
The synthetic route of the natural product Scleropentadide A is as follows: (wherein, Compound 3 is 2-Furanoboric acid)
Figure BDA0002694911630000051
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
compared with the prior synthesis method, the method adopted in the scheme of the invention has great improvement on the yield of the natural product Scleropentadide A, the total yield of the whole synthesis process reaches more than 69 percent, and the yield of gram level can be achieved.
In the prior art, toxic and difficultly obtained chemical reagents are used in the process of synthesizing the natural product Scleropentadide A, and the reagents used in the technical scheme of the invention are nontoxic and easily obtained.
The common procedure in the prior art for deprotecting is to use I2And an oxidizing agent H2O2In the drug synthesis, the residue of the iodine reagent has certain harm to human body, and the hydrogen peroxide also has certain condition requirements in the aspect of treatment.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 1;
FIG. 2 is a nuclear magnetic carbon spectrum of Compound 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of Compound 2;
FIG. 4 is a nuclear magnetic carbon spectrum of Compound 2;
FIG. 5 is a nuclear magnetic hydrogen spectrum of Compound 4;
FIG. 6 is a nuclear magnetic carbon spectrum of Compound 4;
FIG. 7 is a nuclear magnetic hydrogen spectrum of Compound 6;
FIG. 8 is a nuclear magnetic carbon spectrum of Compound 6;
FIG. 9 is a nuclear magnetic hydrogen spectrum of Compound 7;
FIG. 10 is a nuclear magnetic carbon spectrum of Compound 7;
figure 11 is a single crystal diffraction of compound 4.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The method comprises the following steps: a dry round bottom flask was charged with the sugar acid 1(500mg,0.92mmol), EDCI (352.3 mg,1.84mmol), HATU (1.40g,3.7mmol) and DIPEA (478.3mg,3.7mmol) and then dried dichloromethane (4mL) as solvent, after stirring for 15 minutes at 0 deg.C Thiophenol (407.6mg,3.7mmol) was added and after complete consumption of the starting sugar acid 1, water and ethyl acetate were added and extracted three times. The organic phase obtained is washed with aqueous NaCl solution, then dried over anhydrous sodium sulfate and the solvent is dried by spinning to obtain the crude product. The crude product was purified by column chromatography eluting with EA/PE 1:20 to give the clean white solid product, thionate 2 (96%, 562.0mg).
(2S,3R,4S,5R,6R)-2-((Phenylthio)carbonyl)-6-((pivaloyloxy)methyl)tetrahyd ro-2H-pyran-3,4,5-triyl tris(2,2-dimethylpropanoate)2；
Figure BDA0002694911630000061
J＝12.5,2.0Hz,1H),4.24–4.04(m,2H),3.82(ddd,J＝ 10.0,4.5,2.0Hz,1H),1.27(s,9H),1.16(s,9H),1.13(s,9H),1.12(s,9H)；13C NMR (101MHz,CDCl3)δ194.3,178.2,177.2,176.8,176.4,135.0,129.7,129.4,126.5, 81.9,76.4,72.9,69.5,67.5,61.5,39.1,38.9,38.9,38.9,27.3,27.2；HRMS(ESI)m/z calcd for C32H47NO10SNa+(M+Na)+660.28129,found 659.28625.
Step two: in N2To a dry reaction flask were added under protective conditions the thionate 2(102.0mg, 0.16mmol), 2-furanboronic acid 3(30.4mg,0.27mmol), CuTC (51.5mg,0.27mmol), Pd2(dba)3(3.0mg,0.003mmol)and P(OEt)3(5.3mg,0.03mmol) and dry tetrahydrofuran (2mL) was added as solvent and the reaction was allowed to react overnight at 25 ℃. Then adding 2mL of ammonia water solution into the system to quench the reaction, adding ethyl acetate (200mL) for extraction, washing the obtained organic phase with saturated NaCl aqueous solution, drying with anhydrous sodium sulfate, spin-drying the solvent, and separating and purifying by column chromatography, wherein the eluent is EA/PE:1: 10. Glycosyl furanone 4 (96%, 92.0mg) was obtained.
(2S,3R,4S,5R,6R)-2-(Furan-2-carbonyl)-6-((pivaloyloxy)methyl) tetrahydro-2H-pyran-3,4,5-triyltris(2,2-dimethylpropanoate)23；
Figure BDA0002694911630000071
5.23(t,J＝9.6Hz,1H),4.50–4.37(m,1H),4.17(td,J＝12.4,3.3Hz,2H),3.84(ddd, J＝10.2,4.6,2.0Hz,1H),1.20(s,9H),1.14(s,9H),1.09(s,9H),1.03(s,9H)；13C NMR(101MHz,CDCl3)δ181.3,177.9,177.2,176.4,176.3,150.2,147.7,120.9, 112.4,80.0,76.7,73.2,69.2,67.4,61.8,38.8,38.8,38.7,38.6,27.2,27.1,27.5,26.9； HRMS(ESI)m/z calcd for C31H46O11Na+(M+Na)+617.29323,found 617.29370.
After the completion of the second step, the next step is to remove the protecting agent (PiV) from the sugar ring to obtain the natural product, Scleropentadide A, but unexpected circumstances appear here, and a lot of experiments show that, by using various methods for removing the protecting group in the prior art, Scleropentadide A with high purity is difficult to obtain, and by-products remain, mainly because the compound 4 is very unstable under alkaline conditions, and the common method for removing the protecting group under alkaline conditions is not suitable here, but the eliminated by-product 7 is generated.
The following control experimental groups:
Figure BDA0002694911630000072
Figure BDA0002694911630000073
as can be seen from the above experimental groups, the conventional methods for removing protective groups all generate by-products 7.
According to the technical scheme, a carbonyl protection scheme is designed, and the elimination activity of ortho hydroxyl is reduced by converting carbonyl into ketal by adopting methanol, so that the elimination reaction is effectively prevented, almost 100% of Scleropentaside A is obtained, and the specific reaction conditions are as follows:
Figure BDA0002694911630000081
step three: at N2To a dry reaction flask under protected conditions was added glycosylfuranone 4(50.0mg, 0.084mmol), trimethoxymethane (1.68mmol) and H2SO4(0.84 uL). Thereafter, another 2mL dry MeOH was added to the reaction and the reaction was allowed to proceed at 25 deg.C until starting material 4 was consumed. Then, adding 5mL of water and 20mL of EA into the system for extraction, washing the obtained organic phase by using a saturated NaCl aqueous solution, drying by using anhydrous sodium sulfate, spin-drying the solvent, and separating and purifying by using column chromatography, wherein an eluent is: EA/PE 1:15, product is unstable yellow oily liquid ketal 5. Since ketal 5 is very unstable and readily decomposes back to the glycosyl furanone 4, it needs to be used directly and quickly for the next reaction.
Step four: dissolving the product obtained in the last step in 2mL of methanol, adding MeONa (13.6mg, 0.25mmol), reacting at room temperature for 4 hours, and adding acidic resin to adjust the pH value of the system to 2 after the raw materials completely react. The resin was then filtered, washed three times with 50mL of methanol and purified by column chromatography, eluent MeOH/DCM:1: 5. The product was a white solid (75% yield over two steps, 16.3 mg.) Scleropentaside A6.
Figure BDA0002694911630000082
9.5Hz,1H),3.65(dd,J＝12.2,4.6Hz,1H),3.32–3.24(m,4H),3.12(td,J＝9.1,4.4 Hz,1H)；13C NMR(101MHz,DMSO-d6)δ184.5,151.4,148.6,121.3,112.7,81.6, 79.6,78.0,71.6,70.0,61.1；HRMS(ESI)m/z calcd for C11H14O7Na+(M+Na)+ 281.06317,found 281.06323.
Control experimental group: the glycosyl furanone 4 is directly subjected to deprotection to obtain almost all elimination products, and the method comprises the following specific steps:
in N2To a dry reaction flask, glycosyl furanone 4(237.6mg,0.4mmol) and NaOMe (88.6mg,1.64mmol) were added under protection, followed by 2mM LEOH as solvent and stirred at room temperature for 4 hours. After the raw materials are completely reacted, adding acidic resin to adjust the pH value of the system to 2. The resin was then filtered, washed three times with 50mL of methanol and purified by column chromatography eluting with MeOH/DCM:1:5 and the product was the eliminated by-product 7 (98% yield over two steps, 94.0 mg).

Claims (9)

1. A method for synthesizing a natural product Scleropentadide A is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out esterification reaction on the glycosyl acid compound and thiophenol to obtain a thiosugar acid ester compound;
2) carrying out coupling-desulfurization reaction on the thiosugar acid ester compound and 2-furanboronic acid to obtain a glycosyl furanone compound;
3) the glycosyl furanone compound and methanol are subjected to carbonyl protection reaction to obtain a ketal compound;
4) carrying out deprotection reaction on the ketal compound to obtain the ketal compound;
the sugar acid compound has the structure of formula 1:
Figure FDA0003501082970000011
the thionate compound has a structure of formula 2:
Figure FDA0003501082970000012
the glycosyl furanone compound has the structure of formula 3:
Figure FDA0003501082970000013
the ketal compound has the structure of formula 4:
Figure FDA0003501082970000014
2. the method for synthesizing a natural product, Scleropentadide A, according to claim 1, wherein: and (3) carrying out esterification reaction on the glycosyl acid compound and the thiophenol under the action of an HATU condensation reagent, a DIPEA coupling reagent and an organic base to obtain the thiosugar acid ester compound.
3. The method for synthesizing a natural product, Scleropentadide A, according to claim 2, wherein:
the molar ratio of the glycosyl acid compound to the organic base is 1: 2-2.3, wherein the organic base is DIPEA;
the molar ratio of the glycosyl acid compound to the HATU condensation reagent to the DIPEA coupling reagent is 1: 4-4.2; the esterification reaction conditions are as follows: reacting for 6-10 hours at room temperature.
4. The method for synthesizing a natural product, Scleropentadide A, according to claim 1, wherein: the said thiosugar acid ester compound and 2-furanboronic acid are reacted in CuTC and Pd2(dba)3Catalyst and P (OEt)3Coupling-desulfurizing reaction is carried out under the action of a desulfurizing agent to obtain the glycosyl furanone compound.
5. The method for synthesizing a natural product, Scleropentadide A, according to claim 4, wherein:
the molar ratio of the thiosugar acid ester compound to the 2-furanboronic acid is 0.16: 0.27-0.3;
thioglyconate compound, CuTC catalyst and Pd2(dba)3The molar ratio of the catalyst is 0.16: 0.27-0.3: 0.003-0.0035;
thioglyconate compounds with P (OEt)3The molar ratio of the desulfurizer is 0.16: 0.03-0.035;
the coupling-desulfurization reaction conditions are as follows: and reacting for 6-16 h at room temperature under the protection of nitrogen.
6. The method for synthesizing a natural product, Scleropentadide A, according to claim 1, wherein: and carrying out condensation reaction on the glycosyl furanone compound and methanol under the catalytic action of a dehydrating agent and an inorganic acid to obtain a ketal compound.
7. The method for synthesizing a natural product, Scleropentadide A, according to claim 6, wherein:
the molar ratio of the glycosyl furanone compound to the dehydrating agent is 1: 20-21; the dehydrating agent is trimethoxy methane;
the conditions of the condensation reaction are as follows: and reacting for 6-12 hours at room temperature.
8. The method for synthesizing a natural product, Scleropentadide A, according to claim 1, wherein: and carrying out deprotection reaction on the ketal compound and sodium methoxide under an acidic condition to obtain the Scleropentadide A.
9. The method for synthesizing a natural product, Scleropentadide A, according to claim 8, wherein: the molar ratio of the ketal compound to the MeONa is 0.84: 0.25-0.27;
the acid condition is that the pH value is 1.8-2.2, and the acid condition is adjusted by acid resin;
the conditions of the deprotection reaction are as follows: reacting for 3-5 hours at room temperature.
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