CN101143858A - Method for selectively acylating hydroxyl group at C(10) and C(2) position of taxanes - Google Patents
Method for selectively acylating hydroxyl group at C(10) and C(2) position of taxanes Download PDFInfo
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Abstract
The invention relates to a preparation method of paclitaxel and other taxanes. By using trifluoromethanesulfonic salt as catalyst, the method is realized by selectively acylating the hydroxyls at C (10) and C (2') of a 10-deacetyl-taxane compound. The produced taxane with acylated hydroxyls at C (10) and C (2') can be used as an important intermidiate for preparing the paclitaxel and other taxanes.
Description
Technical field:
The present invention relates to the preparation method of a kind of taxol and other Taxan; relate in particular under the catalytic condition of fluoroform sulphonate; go acetyl-bearing taxanes to be converted into the Taxan of C (10) and C (2 ') position acylated hydroxy 10-by a step selectively acylating reaction, and the latter can be used as the important intermediate for preparing taxol and analogue thereof.
Background technology:
Taxol (Paclitaxel, formula II, 1) and Docetaxel (Docetaxel) currently are widely used in the different sorts tumor treatment as a clinical line medication.
Formula II taxol, 10-go acetyl-taxol and 10-to remove acetyl-baccatin III
Extract culture plant cell, biosynthesizing by Chinese yew genus plants, means such as fungi fermentation and chemistry are semi-synthetic can obtain a large amount of 10-and remove acetyl-bearing taxanes, remove acetyl-taxol (formula II, 2) as 10-, 10-removes acetyl-baccatin III (10-DAB, formula II, 3) etc.Can obtain taxol (Taxol) or other bearing taxanes of high antitumour activity by the hydroxyl of acidylate C (10) position.Acidylate work at such Taxan at present mainly concentrates on following two aspects:
(1) adopt acid binding agent catalytie esterification 10-to remove acetyl-taxol (alkane)
People such as Rao (J.Heterocycl.Chem., 1997,34, pp.675) utilize periodate oxidation cracking C (7) position xylosyl, pyridine as the condition of acid binding agent under after the glycoloylization with C (10) and C (2 ') position, slough residual group on C (7) position with phenylhydrazine again, thereby obtain the acetylizad taxol in C (2 ') position, use dimethylamine selective hydrolysis C (2 ') position ethanoyl promptly to obtain taxol (US5200534; US5367086).
People such as Sisti (US5914411) go the acetyl baccatin III to be dissolved in the THF reaction system 10-, and the hydroxyl to wherein adding lithium salts activation C (10) position adds TEA again and makes acid binding agent, and Acetyl Chloride 98Min. has optionally obtained baccatin III as acylating agent.Its subsequently patent (US6048990, US6066749) in, they expand to this method after C (2 ') position hydroxyl is protected, highly selective acylation C (10) position hydroxyl obtains the protected taxol of C (2 ') position hydroxyl.
People such as Chattopadhyay (US5856532) will obtain 10-and remove the acetyl taxane compounds; after silicon ether is protected the hydroxyl of its C (7) and C (2 ') position; acetylize C (10) position hydroxyl under the condition that pyridine exists again, last desiliconization ether protecting group obtains target product.
People such as Fang (chemical wall bulletin, 8 (10), 1997, pp.847) find that 7-table-10-goes C in acetyl-taxol (7) hydroxyl at pyridine, is difficult to be acetylation under the condition of Acetyl Chloride 98Min..Therefore, they protect C (2 ') position hydroxyl with chlorotriethyl silane, acetylize C (10) position hydroxyl under pyridine catalysis, slough C (2 ') position silicon ether protecting group after, obtain 7-table-taxol.
(2) adopt Lewis acid catalysis acidylate 10-to remove acetyl-taxol (alkane)
Holton etc.) people (Tetrahedron Letters; 1998,39, pp.2883) find; Lewis acid is being arranged; as cerous compounds, zinc chloride is under the situation that tin chloride etc. exist; taxol after going acetyl crust card booth II I or C (2 ') position hydroxyl protected for 10-; the hydroxyl that the hydroxyl of C (10) position can have precedence over C (7) position by the selectivity acidylate (CN125196C, WO1999/009021, US6706896).But in its research work, do not relate to that to have the Taxan of free hydroxyl with C (2 ') position be raw material, the problem of acidylate C (2 ') position hydroxyl.
People such as Damen (TetrahedronLetters, 1998,39, pp.6081) find, under the fluoroform sulphonate catalysis of rare earth element, adopt diacetyl oxide can with 10-DAB optionally acetyl turn to baccatin III.If adopt other acid anhydrides, by C (10) the position hydroxyl of selectively acylating 10-DAB, can obtain different derivatives (EP0875508, US5874595, JP10298171).Yet in its research work, do not relate to the Taxan that there is side chain in C (13) position, do not relate to C under this reaction conditions (1) yet, C (7), C (10), the selectively acylating problem between each hydroxyl of C (2 ') position.
People such as Tang Dingning (CN1640871A; WO2005/073209) find in reaction system, to contain rare earth chloride; rare earth hydrate; the oxychlorination rare earth; or during the double sulphate of rare earth element; can adopt diacetyl oxide to come highly selective acylation 10-to remove acetyl-taxol C (10) and C (2 ') position hydroxyl, slough C (2 ') position ethanoyl again and can obtain taxol.
The fluoroform sulphonate of IIIB family metallic element is the novel acylation reaction catalyst of developing in recent years of a class (Yamamoto et al., J.Am.Chem.Soc., 1995,117,4413).For in C (1), C (7), C (10), there is the Taxan of a plurality of hydroxyls in C (2 ') position, investigates its catalytic activity to each acylated hydroxy reaction and is still a job that needs to be resolved hurrily.
Technology contents:
The object of the present invention is to provide and a kind ofly go the acetyl bearing taxanes to be converted into the taxol of C (10) and C (2 ') position acylated hydroxy or the preparation method of other Taxan 10-.The invention particularly relates to Taxan in C (1), C (10) and C (2 ') all contain hydroxyl in the position, and C (7) position can contain in the time of also can not containing free hydroxyl, use acylating agent optionally with C (10) and C (2 ') hydroxyl reaction.
Concrete enforcement of the present invention be by with the fluoroform sulphonate of IIIB family metallic element as catalyzer; in inert organic solvents, go acetyl-taxol (alkane) raw material to mix with 10-; under the condition of acid anhydrides as acylating agent; these catalyzer can optionally activate C (10) and C (2 ') position hydroxyl, thereby make C (10) and C (2 ') position hydroxyl prior to C (1) and hydroxyl position, C (7) position acidylate.Simultaneously, protected or when being replaced when C (1) and C (7) position hydroxyl by other group, adopt method of the present invention, also can obtain the Taxan of C (10) and C (2 ') acylated hydroxy.And the latter can obtain taxol or other Taxan by selective hydrolysis C (2 ') position acyl group under the alkaline condition.
This selectively acylating reaction is preferably carried out in ether solvent, as tetrahydrofuran (THF), and ether etc.But at methylene dichloride, chloroform, reaction also can take place in the good solvent of Taxans such as ethyl acetate, and just the reaction times slightly prolongs.This reaction system is preferably the solvent that strictness dewaters, and when the moisture in the system surpasses when a certain amount of, can reduce speed of response, even cause reaction to carry out.
This selectively acylating reacts the catalyzer that is adopted, and comes from the fluoroform sulphonate of IIIB family metallic element in the periodic table of elements.Preferably from the trifluoromethanesulfonic acid scandium, Ytterbiumtriflate, trifluoromethanesulfonic acid erbium, trifluoromethanesulfonic acid lanthanum, trifluoromethanesulfonic acid rubidium, trifluoromethanesulfonic acid samarium, trifluoromethanesulfonic acid dysprosium.
The reaction of this selectively acylating at room temperature can be carried out smoothly, helps reaction and reaches balance as early as possible but suitably heat up, and general preferably carries out at-80 ℃ to 100 ℃.
Described 10-goes acetyl-Taxan to have the structure of following general formula I
Formula I
Wherein R1 is-H ,-OR ,-OSi (R) 3 or-OCOR; R2 and R3 can be the same or different, and are-H ,-R or-OR; Wherein R is H, the straight chain of C1 to C20, side chain or ring-like alkyl, and aryl, aralkyl, and the substituent of above-mentioned three kinds of alkyl, substituting group comprises hydroxyl, the alkoxyl group of C1 to C8, acetal, ketal, halogen, nitro and amino.
Especially, acetal as referred to herein and ketal partly have general structure
X1 wherein; X2; X3; X4 acute pyogenic infection of finger tip hydrogen or alkyl, and alkyl can replace by any substituting group defined herein, and this part can comprise from carbohydrate or replace acetal or the ketal (KoppakaV.Rao that carbohydrate such as glucose or wood sugar are made; J.Heterocyclic Chem.34; 676 (1997)), when the protecting group that is used as C (7) position hydroxyl when this part enters in the Taxan of the present invention, X1 or X2 acute pyogenic infection of finger tip Taxan part.
The acylating agent that can be used for this selectively acylating reaction comprises various acid anhydrides, for example, diacetyl oxide, sym-dichloroacetic anhydride, trifluoroacetic anhydride, benzoyl oxide etc., the structure of described acid anhydrides has general structure
Wherein R ' is straight chain, side chain or the ring-like alkyl of C1 to C20, aryl, and the halides of above-mentioned three kinds of alkyl.
Technical process of the present invention and chemical reaction general formula are shown in formula III.
R1 wherein, R2, R3, R ' definition is the same.
Formula III
Taxan raw material involved in the present invention can be natural product source in C (10), the 10-that C (2 ') contains the position hydroxyl simultaneously removes acetyl-bearing taxanes monomer or its mixture.Simultaneously, via biosynthesizing, the Taxan that contains hydroxyl in above-mentioned position that the semi-synthetic or complete synthesis means of chemistry obtain also can adopt the present invention that C (10) and C (2 ') position hydroxyl are carried out selectively acylating.
Description of drawings:
Fig. 1 removes the LC-MS spectrogram of acetyl-taxol for 10-, and 10-removes the negative ion signal of acetyl-taxol: [M-H]
-At m/z810.4;
Fig. 2 is the LC-MS spectrogram of 2 '-ethanoyl-taxol, the negative ion signal of 2 '-ethanoyl-taxol: [M-H]
-At m/z894.9;
Fig. 3 is the LC-MS spectrogram of taxol, the negative ion signal of taxol: [M-H]
-At m/z 852.3;
Fig. 4 removes the LC-MS spectrogram of acetyl-Cephalomannine for 10-, and 10-removes the negative ion signal of acetyl-Cephalomannine: [M-H]
-At m/z 788.3;
Fig. 5 is the LC-MS spectrogram of Cephalomannine, the negative ion signal of Cephalomannine: [M-H]
-At m/z830.4;
Fig. 6 removes the LC-MS spectrogram of acetyl-7-wood sugar-taxol for 10-; 10-removes the negative ion signal of acetyl-7-wood sugar-taxol: [M-H]
-At m/z942.5.
Embodiment:
The following example is in order to further specify the present invention, rather than will limit its scope.
Take by weighing 10-and remove acetyl-taxol (content 90%, the LC-MS spectrogram is seen Fig. 1) sample be dissolved in the reaction solvent, the fluoroform sulphonate that adds the normal IIIB of catalysis family metallic element, behind the thorough mixing, slowly drip about 3 normal diacetyl oxides, stir under the room temperature, after the TLC detection reaction is complete, adds saturated NaHCO3 solution and extinguish reaction.Reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam 2 '-ethanoyl-taxol (the LC-MS spectrogram is seen Fig. 2).The various catalyzer that adopted, catalytic amount, reaction solvent, reaction times and yield see Table 1.
Many kinds of fluoroform sulphonate catalytie esterifications of table 1 10-removes acetyl-taxol
| Catalyzer | Catalytic amount (equiv) | Reaction solvent | Reaction times (h) | Yield (%) |
| Sc(OTf)3 Sc(OTf)3 La(OTf)3 Yb(OTf)3 Yb(OTf)3 Yb(OTf)3 Er(OTf)3 | 0.2 1.0 0.1 0.1 0.5 0.2 0.1 | THF CHCl3 THF THF CH2Cl2 EtOAc THF | 3.0 36 1.5 1.5 36 10 1.0 | ＞98 85 ＞98 ＞98 80 ＞98 ＞98 |
| Nd(OTf)3 Sm(OTf)3 Dy(OTf)3 | 0.1 0.1 0.1 | THF THF THF | 1.5 1.0 1.5 | ＞98 ＞98 ＞98 |
Embodiment 2 goes acetyl-taxol to produce taxol from 10-
Take by weighing 10-and remove the sample 1g of acetyl-taxol (content 77%, the LC-MS spectrogram is seen Fig. 1), be dissolved in the 20ml tetrahydrofuran (THF), after adding 0.07g Ytterbiumtriflate thorough mixing, slowly drip the 0.35ml diacetyl oxide, reaction is 1.5 hours under the room temperature, adds saturated NaHCO3 solution 25ml and extinguishes reaction.Reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam the 1.05g white solid.It is dissolved in the dimethylamine methanol solution of 50ml0.1%, under the room temperature reaction 1h after, use the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.95g white solid.This material gets 0.61g taxol (the LC-MS spectrogram is seen Fig. 3 for content 90%, yield 67.8%) behind silica gel column chromatography.
Embodiment 3 goes acetyl-Cephalomannine to produce Cephalomannine from 10-
Take by weighing 10-and remove acetyl-Cephalomannine (content 85%, the LC-MS spectrogram is seen Fig. 4) sample 1g, be dissolved in the 20ml tetrahydrofuran (THF), after adding 0.08g Ytterbiumtriflate thorough mixing, slowly drip the 0.35ml diacetyl oxide, reaction is 1.5 hours under the room temperature, adds saturated NaHCO3 solution 25ml and extinguishes reaction.Reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam the 0.93g white solid.It is dissolved in the dimethylamine methanol solution of 50ml0.1%, under the room temperature reaction 1h after, use the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.86g white solid.This material obtains 0.77g Cephalomannine (the LC-MS spectrogram is seen Fig. 5 for content 90%, yield 77.4%) behind silica gel column chromatography.
Embodiment 4 goes acetyl-7-wood sugar-taxol to produce taxol from 10-
Take by weighing 10-and remove the sample 1g of acetyl-7-wood sugar-taxol (content 90%, the LC-MS spectrogram is seen Fig. 6), be dissolved in the 50ml methanol (4: 1), add 0.9g sodium periodate and 3ml0.5M sulfuric acid after, reaction is 5 hours under the room temperature.Add 50ml water and extinguish reaction, reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam the 0.98g white solid.It is dissolved in the 20ml tetrahydrofuran (THF), behind the adding 0.08g Ytterbiumtriflate, slowly drips the 0.3ml diacetyl oxide, reaction is 1 hour under the room temperature, adds saturated NaHCO3 solution 25ml and extinguishes reaction, the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 1.03g white solid.It is dissolved in the 20ml methanol (4: 1), adds 3ml acetate and 0.5ml phenylhydrazine, 50 ℃ down reaction add 50ml water and extinguish reaction after 3 hours, the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.95g white solid.It is dissolved in the dimethylamine methanol solution of 50ml0.1%, under the room temperature reaction 1h after, use the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.92g white solid.This material obtains 0.53g taxol (the LC-MS spectrogram is seen Fig. 3 for content 90%, yield 58.6%) behind silica gel column chromatography.
Embodiment 5 goes acetyl-taxol to produce 10-benzoyl-10-from 10-and removes the acetyl taxol
Take by weighing 10-and remove the sample 1g of acetyl taxol (content 77%, the LC-MS spectrogram is seen Fig. 1), be dissolved in the 20ml tetrahydrofuran (THF), 0.08g behind the Ytterbiumtriflate thorough mixing, add the 0.5g benzoyl oxide, 50 ℃ were reacted 3 hours down, add saturated NaHCO3 solution 25ml and extinguish reaction.Reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam the 0.91g white solid.It is dissolved in the dimethylamine methanol solution of 50ml0.1%, under the room temperature reaction 1h after, use the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.87g white solid.This material obtains 0.72g10-benzoyl-10-and removes acetyl taxol (content 85%, yield 69.3%) behind silica gel column chromatography.
Embodiment 6 goes acetyl-7-O-Troc-taxol to produce 10-trifluoroacetyl-10-from 10-and removes acetyl-7-O-Troc-taxol
Take by weighing 10-and remove the sample 0.5g of acetyl-7-O-Troc-taxol (content 78%), be dissolved in the 10ml tetrahydrofuran (THF), add 0.03g trifluoromethanesulfonic acid lanthanum thorough mixing after, add the 0.3g trifluoroacetic anhydride, 20 ℃ of reactions 0 down.5 hours, add saturated NaHCO3 solution 15ml and extinguish reaction.Reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam the 0.52g white solid.This material is dissolved in the dimethylamine methanol solution of 25ml0.1%, under the room temperature reaction 1h after, use the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.49g white solid.This material obtains 0.37g10-trifluoroacetyl-10-and removes acetyl-7-O-Troc-taxol (content 85%, yield 74.4%) behind silica gel column chromatography.
Embodiment 7 goes acetyl-7-O-TES-taxol to produce 10-propionyl-10-from 10-and removes acetyl-7-O-TES-taxol
Take by weighing 10-and remove the sample 0.5g of acetyl-7-O-TES-taxol (content 80%), be dissolved in the 10ml tetrahydrofuran (THF), add 0.03g trifluoromethanesulfonic acid scandium, behind the thorough mixing, add the 1.0ml propionic anhydride, 30 ℃ were reacted 1.5 hours down, add saturated NaHCO3 solution 15ml and extinguish reaction.Reaction back feed liquid ethyl acetate extraction, anhydrous sodium sulfate drying, vacuum revolve steam the 0.57g white solid.This material is dissolved in the dimethylamine methanol solution of 25ml0.1%, under the room temperature reaction 1h after, use the ethyl acetate extraction feed liquid, anhydrous sodium sulfate drying, vacuum revolve steam the 0.52g white solid.This material obtains 0.38g10-propionyl-10-and removes acetyl-7-O-TES-taxol (content 80%, yield 71.5%) behind silica gel column chromatography.
Claims (7)
- A selectively acylating taxone C (10) and C (2 ') position hydroxyl method, it is characterized in that:---contain the normal fluoroform sulphonate of catalysis in the reaction system as catalyzer;---use to be no less than 2 moles of normal acid anhydrides of substrate as acylating agent, the 10-that processing has following general structure (formula I) removes acetyl-bearing taxanes, thereby obtains the Taxan of C (10) and C (2 ') position acidylate;Formula IWherein R1 is-H ,-OR ,-OSi (R) 3 or-OCOR; R2 is identical with R3 or different, is-H ,-R or-OR; Described R is H, the straight chain of C1 to C20, side chain or ring-like alkyl, and aryl, aralkyl, the substituent of perhaps above-mentioned three kinds of alkyl, substituting group comprises hydroxyl, the alkoxyl group of C1 to C8, acetal, ketal, halogen, nitro or amino;---reaction process is carried out in inert organic solvents.
- 2. according to the method for the described selectively acylating taxone C of claim 1 (10) and C (2 ') position hydroxyl; it is characterized in that: described Taxan raw material be natural product source in C (10); the 10-that C (2 ') contains the position hydroxyl simultaneously removes acetyl-bearing taxanes monomer or its mixture; perhaps via biosynthesizing, the Taxan that contains hydroxyl in above-mentioned position that the semi-synthetic or complete synthesis means of chemistry obtain.
- 3. according to the method for described selectively acylating taxone C of claim 1 (10) and C (2 ') position hydroxyl, it is characterized in that: described catalyzer is the fluoroform sulphonate of IIIB family metallic element.
- 4. according to the method for the described selectively acylating taxone C of claim 3 (10) and C (2 ') position hydroxyl; it is characterized in that: described catalyzer is selected from the trifluoromethanesulfonic acid scandium; Ytterbiumtriflate; the trifluoromethanesulfonic acid erbium; the trifluoromethanesulfonic acid lanthanum; the trifluoromethanesulfonic acid rubidium, trifluoromethanesulfonic acid samarium, trifluoromethanesulfonic acid dysprosium.
- 5. according to the method for described selectively acylating taxone C of claim 1 (10) and C (2 ') position hydroxyl, it is characterized in that: the structure of described acid anhydrides has general structureWherein R ' is straight chain, side chain or the ring-like alkyl of C1 to C20, aryl, and the halides of above-mentioned three kinds of alkyl.
- 6. according to the method for described selectively acylating taxone C of claim 1 (10) and C (2 ') position hydroxyl, it is characterized in that: described inert organic solvents is selected from tetrahydrofuran (THF), ether; ethyl acetate; dioxane, chloroform, the mixed system of one or more in the methylene dichloride.
- 7. according to the method for described selectively acylating taxone C of claim 1 (10) and C (2 ') position hydroxyl, it is characterized in that: described temperature of reaction is-80 ℃ to 100 ℃.
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| CN111848623A (en) * | 2019-04-25 | 2020-10-30 | 中国科学院大连化学物理研究所 | Method for synthesizing fluorine-containing chiral ketal amine by catalysis of chiral phosphoric acid |
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| CN1281509C (en) * | 2004-01-13 | 2006-10-25 | 中国科学院过程工程研究所 | Method for preparing zirconium phosphate |
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| CN111848623A (en) * | 2019-04-25 | 2020-10-30 | 中国科学院大连化学物理研究所 | Method for synthesizing fluorine-containing chiral ketal amine by catalysis of chiral phosphoric acid |
| CN111848623B (en) * | 2019-04-25 | 2021-11-12 | 中国科学院大连化学物理研究所 | Method for synthesizing fluorine-containing chiral ketal amine by catalysis of chiral phosphoric acid |
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Effective date of registration: 20180228 Address after: 215600 A 207 room A building center of Zhangjiagang Free Trade Zone, Suzhou Free Trade Zone, Jiangsu Patentee after: Zhangjiagang Institute of industrial technology, Dalian Institute of Chemical Physics, China Academy of Sciences Address before: 116023 Zhongshan Road, Liaoning, No. 457, Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
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