CN102824927A - Method for preparing solid supported trimethylsilyl trifluoromethanesulfonate and application thereof - Google Patents
Method for preparing solid supported trimethylsilyl trifluoromethanesulfonate and application thereof Download PDFInfo
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- CN102824927A CN102824927A CN2011101596189A CN201110159618A CN102824927A CN 102824927 A CN102824927 A CN 102824927A CN 2011101596189 A CN2011101596189 A CN 2011101596189A CN 201110159618 A CN201110159618 A CN 201110159618A CN 102824927 A CN102824927 A CN 102824927A
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- solid supported
- sulfonic acid
- acid ester
- tmsotf
- selectively removing
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- 0 *CC([C@@](C1OC(c2ccccc2)=O)OC(c2ccccc2)=O)O[C@](*)C1OC(c1ccccc1)=O Chemical compound *CC([C@@](C1OC(c2ccccc2)=O)OC(c2ccccc2)=O)O[C@](*)C1OC(c1ccccc1)=O 0.000 description 2
Abstract
The invention belongs to the field of chemical synthesis of drugs and relates to a method for preparing solid supported trimethylsilyl trifluoromethanesulfonate TMSOTf and an application thereof. The method comprises the following steps of: suspending a solid supported reagent on a preparation solvent, violently stirring, slowly adding trimethylsilyl trifluoromethanesulfonate drop by drop, stirring at room temperature, steaming to remove the solvent at reduced pressure to obtain a fluid solid powder, and activating at the temperature of 100 DEG C for 24h to prepare the solid supported trimethylsilyl trifluoromethanesulfonate. The method provided by the invention can be used in carbohydrate chemistry acetylation, isopropylation, benzalation, selective removal of isopropylidene, selective removal of triphenylmethyl, selective removal of tetrahydropyran and selective removal of silyl-ethers or glycosylation operation. The method provided by the invention is simple and easy to operate, has low toxicity, can be used to significantly reduce the stress caused by chemical synthesis to the environment, is suitable for large-scale industrial production, and can provide support for large-scale synthesis and screening of carbohydrate drugs.
Description
Technical field
The invention belongs to the synthetic field of pharmaceutical chemistry, relate to a kind of the prepare method of solid supported trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf) and the application in carbohydrate chemistry thereof, be particularly useful for important intermediate synthetic of the saccharide compound of biologically active.
Background technology
Natural oligosaccharides or glycoconjugate have good biologically active aspect physiology and the pharmacology, receive the close concern of People more and more.Up to the present, about existing a large amount of bibliographical information of synthesizing of saccharide compound.The building-up process that prior art discloses saccharide compound is selective protection, selectivity deprotection and the corresponding glucosides process of hydroxyl.Wherein, the isopropylideneization of full acetylated, the o-dihydroxy of monose and benzal turn into for the selective protection operation utilization of the building-up process of saccharide compound comparatively frequent; In like manner, the selectively removing of selectively removing isopropylidene, selectively removing trityl, selectively removing THP trtrahydropyranyl and selectively removing silicon ether protection base has a wide range of applications in the operation of selectivity deprotection; Last glucosidesization is the most key synthesis step of building-up process of saccharide compound.Selective protection, selectivity deprotection and glucosides method about saccharide compound are more; Up to the present; There are some following defectives in these methods: or agents useful for same costliness very; Toxicity is very big, and environment has been caused great pollution, has seriously run counter to the present strategy of sustainable development of advocating.Based on this, seek a kind of simple to operation, environmental friendliness, toxicity low, be applicable to that large-scale industrial production carbohydrate medicine synthetic method causes the relevant researcher's in this area concern.
Summary of the invention
The objective of the invention is to overcome deficiency and the defective that prior art exists, the preparation method of a kind of solid supported trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf) is provided.
Further purpose of the present invention provides the application of described method in carbohydrate chemistry is synthetic.
The invention provides TMSOTf-SiO
2Catalyst system and catalyzing can be realized all operations of selective protection, selectivity deprotection and glucosides process about saccharide compound efficiently.The inventive method is simple to operation, environmental friendliness, toxicity are low, be applicable to large-scale industrial production, can be the extensive synthetic strong support that provides of carbohydrate medicine.
Particularly; The preparation method of a kind of solid supported trimethyl silicane trifluoromethayl sulfonic acid ester of the present invention is characterized in that it comprises: the solid supported agent is suspended in the preparation solvent; Slowly drip trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf) under the vigorous stirring; Drip the back stirring at room, remove solvent to mobile pressed powder under reduced pressure, 100 ℃ of following activation 24h make solid supported trimethyl silicane trifluoromethayl sulfonic acid ester.
Among the present invention, described solid supported agent is selected from silica, aluminium oxide (comprising acidity, alkalescence and neutrality), imvite, diatomite and potter's clay etc., and in one embodiment of the present of invention, preferred silica is the solid supported agent, wherein, TMSOTf-SiO
2Consumption be between the 0.1%-200% of reaction substrate.
Among the present invention, the size of solid supported agent is the 1-1000 order, and preferred 200-300 purpose silica is the solid supported agent in one embodiment of the present of invention.
Among the present invention, the preparation solvent is selected from ether, carrene, acetonitrile or oxolane.In one embodiment of the present of invention, the preferred for preparation solvent is an absolute ether.
Among the present invention, activation temperature is between 0 ℃-200 ℃.
Among the present invention, the load capacity of TMSOTf is between 0.001-10mmol/g.
Among the present invention, reaction temperature is between 0 ℃-200 ℃.
Among the present invention, the reaction time is between 1s-200h.
The preparation method of solid supported trimethyl silicane trifluoromethayl sulfonic acid ester of the present invention (TMSOTf) is used in carbohydrate chemistry acetylation, isopropylideneization, benzalization, selectively removing isopropylidene, selectively removing trityl, selectively removing THP trtrahydropyranyl, selectively removing silicon ether and the glucosidesization.
The advantage for preparing the method for solid supported trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf) of the present invention has:
1, this method is practical, and simple to operation, toxicity is low;
2, can obviously reduce the pressure that chemical synthesis causes to environment;
3, be applicable to large-scale industrial production;
4, can strong support be provided for the extensive synthetic and screening of carbohydrate medicine.
For the ease of understanding, below will describe in detail the method for preparing solid supported trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf) of the present invention through concrete embodiment.What need particularly point out is; Instantiation only is in order to explain; Obviously those of ordinary skill in the art can explain according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.
The specific embodiment
In the embodiments of the invention,
1H NMR,
13C NMR by Bruker ARX 400 at CDCl
3In record, be interior mark with tetramethylsilane.Mass spectrum adopts VG PLATFORM mass spectrograph, with ESI technology sample introduction.Thin-layer chromatography (TLC) is by HF
254Sulfuric acid methanol solution or ultraviolet (UV) detector with 30% (v/v) on the silica gel plate detect.Column chromatography adopts 200-300 order silica gel, and as eluent, solution is less than 60 ℃ of following decompression distillation with petroleum ether-ethyl acetate, but below the compound that do not specify be and be purchased or the reference literature preparation.
Embodiment 1: prepare silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf)
In the 500mL round-bottomed flask 45g 200-300 order silica gel is suspended in the 200mL absolute ether, slowly drips 14.2mL trimethyl silicane trifluoromethayl sulfonic acid ester (TMSOTf) under the vigorous stirring.After dropwising stirring at room 1h, remove solvent to mobile pressed powder under reduced pressure.100 ℃ of following activation 24h can make the silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid of 1.25mmol/g ester.
Embodiment 2: the catalysis of silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester is full acetylated
(18.0g 100mmol) is suspended in Ac with D-glucose 1
2(55mL 550mmol), repeatedly adds TMSOTf-SiO to O on a small quantity under the ice bath
2(0.4g, o.5mmol).(benzinum: ethyl acetate=2: 1) detection reaction is complete, adds the ethyl acetate dilution for TLC behind the 10min.Filter the back and use saturated NaHCO
3Neutralization is collected organic facies, anhydrous Na
2SO
4Drying concentrates, column chromatography get compound 2 (38.9g, 99mmol), yield 99%.The molecular weight of mass spectral analysis compound 2 is 309.2.
Embodiment 3: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalysis isopropylideneization
(1.8g 10.0mmol) is suspended in dry acetone (50mL), adds TMSOTf-SiO under the reflux with D-galactolipin 3
2(0.4g, o.5mmol).(benzinum: ethyl acetate=2: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 10min.Filter, concentrate, column chromatography get compound 4 (2.1g, 8.1mmol), yield 81%.
1H?NMR(400MHz,CDCl
3):δ1.33(s,6H,2×CH
3),1.45(s,3H,CH
3),1.53(s,3H,CH
3),2.34(br,1H,OH),3.74(m,1H),3.81-3.84(m,2H),4.28(d,J7.8Hz,1H),4.33(d,J0.8Hz,1H),4.61(d,J7.8Hz,1H),5.56(d,J4.3Hz,1H,H-1).
Embodiment 4: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalysis benzal baseization
(2.86g, 10.0mmol), (1.5mL 15mmol) is dissolved in dry acetonitrile (50mL) to PhCHO, adds TMSOTf-SiO under the reflux with compound 5
2(0.4g, o.5mmol).(benzinum: ethyl acetate=2: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 10min.Filter, concentrate, column chromatography get compound 6 (3.21g, 8.6mmol), yield 86%.
1H?NMR(400Hz,CDCl
3):δ7.35-7.48(m,7H),7.15(d,2H),6.83(d,2H),5.53(s,1H),4.57(d,J9.6Hz,1H),4.36-4.39(dd,J3.6Hz,10.0Hz,1H),3.75-3.85(m,2H),3.41-3.52(m,3H),2.70(s,1H,OH),2.60(s,1H,OH),2.36(s,3H,CH
3).
Embodiment 5: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalytic selectivity removes isopropylidene
(3.50g 10.0mmol) is dissolved in methyl alcohol (50mL), stirs to add TMSOTf-SiO down with compound 7
2(0.4g, o.5mmol).(benzinum: ethyl acetate=1: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 30min.Filter, concentrate, column chromatography get compound 8 (2.79g, 9.0mmol), yield 90%.
1H?NMR(400MHz,CDCl
3):δ1.33(s,3H,CH
3),1.49(s,3H,CH
3),3.68-3.72(dd,J5.4Hz,14.0Hz,1H),3.79-3.83(dd,J3.6Hz,11.7Hz,1H),4.01-4.05(m,1H),4.10-4.14(m,2H),4.55(d,J11.7Hz,1H),4.64(d,J3.9Hz,1H),4.74(d,J11.7Hz,1H),5.95(d,J3.9Hz,1H,H-1),7.26-7.40(m,5H).
Embodiment 6: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalytic selectivity removes trityl
(8.40g 10.0mmol) is dissolved in methyl alcohol (50mL), stirs to add TMSOTf-SiO down with compound 9
2(0.4g, o.5mmol).(benzinum: ethyl acetate=3: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 30min.Filter, concentrate, column chromatography get compound 10 (5.62g, 9.4mmol), yield 94%.
1H?NMR(400Hz,CDCl
3):δ8.13-7.25(m,15H,3×Ph-H),6.92(d,2H),6.83(d,2H),5.90(dd,J3.6Hz,10.4Hz,1H,H-2),5.84(d,J3.2Hz,1H,H-4),5.59(dd,J3.2Hz,10.4Hz,1H,H-3),4.87(d,J8.0Hz,1H,H-1),4.05-4.03(m,1H,H-5),3.97-3.78(m,2H,H-6),3.65(s,3H,CH
3O).
Embodiment 7: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalytic selectivity removes THP trtrahydropyranyl
(3.75g 10.0mmol) is dissolved in methyl alcohol (50mL), stirs to add TMSOTf-SiO down with compound 11
2(80.0mg, o.1mmol).(benzinum: ethyl acetate=4: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 30min.Filter, concentrate, column chromatography get compound 12 (2.84g, 9.8mmol), yield 98%.
1HNMR(400MHz,CDCl
3)δ3.59(dd,J13.3Hz,8.6Hz,1H),2.43(dd,J19.0Hz,8.6Hz,1H),2.12-1.99(m,1H),1.91(dd,J15.5Hz,10.6Hz,1H),1.78(d,J10.8Hz,3H),1.74-1.62(m,2H),1.48(m?5H),1.26(m,6H),1.20-1.03(m,1H),0.96(m,2H),0.85(s,3H),0.82(s,3H),0.67(m,1H);
13C?NMR(125MHz,CDCl
3):12.2,13.8,20.5,21.7,26.5,28.4,30.9,31.4,31.5,35.0,35.6,35.8,36.9,38.0,44.8,47.7,51.4,54.4,71.1,221.3.
Embodiment 8: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalytic selectivity removes silicon ether
(7.95g 10.0mmol) is dissolved in acetonitrile (50mL), stirs to add TMSOTf-SiO down with compound 13
2(0.8mg, 1mmol).(benzinum: ethyl acetate=4: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 2h.Filter, concentrate, column chromatography get compound 14 (5.34g, 9.6mmol), yield 96%.
1H?NMR(400MHz,CDCl
3)δ7.48-7.24(m,15H),6.99(d,J8.9Hz,2H),6.81(d,J8.9Hz,2H),5.42(s,1H),4.99(dd,J20.9Hz,11.6Hz,2H),4.85(dd,J16.9Hz,12.0Hz,2H),4.71(dd,J23.0Hz,11.8Hz,2H),4.18(dd,J23.0Hz,10.0Hz,2H),3.97(d,J16.4Hz,2H),3.77(s,3H),3.69(d,J10.9Hz,1H),3.49(s,1H);
13C?NMR(125MHz,CDCl
3)δ155.24,151.05,138.82,138.47,138.23,128.81,128.72,128.67,128.60,128.26,128.17,127.97,127.86,127.75,118.71,114.70,97.60,79.16,77.55,77.23,76.91,76.48,74.99,74.73,73.79,73.66,71.24,62.42,55.79.
Embodiment 9: silicon dioxide carried trimethyl silicane trifluoromethayl sulfonic acid ester catalysis glycosylation reaction
(3.99g, 6.6mmol) (2.65g 5.5mmol) is dissolved in dry carrene (45mL), and-10 ℃ of argon shields add TMSOTf-SiO down with compound 16 with compound 15
2(52.8mg, 0.066mmol).(benzinum: ethyl acetate=4: 1) detection reaction is complete, adds the triethylamine cessation reaction for TLC behind the 2h.Filter, concentrate, column chromatography gets compound 14 (4.43g, 4.8mmo l), yield 88%.
1H?NMR(400MHz,CDCl
3):δ1.26(d,J5.6Hz,3H,CH
3),1.33(d,J5.9Hz,3H,CH
3),3.80(s,3H,OCH
3),4.23-4.32(m,2H),4.47-4.49(m,3H,H-2),5.03-5.19(m,2H),5.26(s,1H),5.50-5.56(m,2H),5.64-5.76(m,4H),5.87(dd,J
2,3=J
3,4=3.6Hz,1H,H-3),6.88-6.91(m,2H,Ar-H),7.09-7.12(m,2H,Ar-H),7.31-7.64(m,12H,Bz-H),7.96-8.20(m,8H,Bz-H);
13C?NMR(125MHz,CDCl
3):16.3,17.6,55.7,65.9,67.6,67.9,68.7,69.2,70.1,71.9,72.4,72.7,98.7(C-1),99.1(C-1),114.8,117.5,118.8,128.4,128.4,128.5,128.6,129.2,129.2,129.3,129.8,129.9,130.1,131.2,133.0,1332,133.3,133.5,150.1,153.9,155.2,164.8,165.5,165.6,166.4.
Claims (10)
1. the preparation method of a solid supported trimethyl silicane trifluoromethayl sulfonic acid ester; It is characterized in that; It comprises: the solid supported agent is suspended in the preparation solvent, slowly drips trimethyl silicane trifluoromethayl sulfonic acid ester under the vigorous stirring, drip the back stirring at room; Remove solvent to mobile pressed powder under reduced pressure, 100 ℃ of following activation 24h make solid supported trimethyl silicane trifluoromethayl sulfonic acid ester.
2. by the described method of claim 1, it is characterized in that described solid supported agent is selected from silica, aluminium oxide, imvite, diatomite or potter's clay.
3. by the described method of claim 2, it is characterized in that described aluminium oxide is acidic alumina, alkali alumina or neutral alumina.
4. by the described method of claim 1, it is characterized in that the load capacity of described TMSOTf is between 0.001-10mmol/g.
5. by the described method of claim 1, it is characterized in that the size of described solid supported agent is the 1-1000 order.
6. by the described method of claim 1, it is characterized in that described solid supported agent is a silica, wherein, TMSOTf-SiO
2Consumption be between the 0.1%-200% of reaction substrate.
7. by the described method of claim 6, it is characterized in that described silica is the 200-300 order.
8. by the described method of claim 1, it is characterized in that described preparation solvent is selected from absolute ether, carrene, acetonitrile or oxolane.
9. by the described arbitrary method of claim 1-8, it is characterized in that described activation temperature is between 0 ℃-200 ℃; Described reaction temperature is between 0 ℃-200 ℃; Reaction time is between 1s-200h.
10. press the purposes of method in carbohydrate chemistry acetylation, isopropylideneization, benzalization, selectively removing isopropylidene, selectively removing trityl, selectively removing THP trtrahydropyranyl, selectively removing silicon ether or glucosidesization of claim 1.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1605391A (en) * | 2004-08-20 | 2005-04-13 | 中国科学院上海有机化学研究所 | Perfluoroalkyl group sulfonic acid and sulfonate carried by macromolecule and its preparation method and application |
CN101239999A (en) * | 2008-03-17 | 2008-08-13 | 江南大学 | Method for preparing alkylglycoside by using solid-carrying heteropolyacid catalyst |
EP2145895A1 (en) * | 2008-07-08 | 2010-01-20 | Commissariat à l'Energie Atomique | Process for the manufacturing of glycochips |
-
2011
- 2011-06-14 CN CN2011101596189A patent/CN102824927A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1605391A (en) * | 2004-08-20 | 2005-04-13 | 中国科学院上海有机化学研究所 | Perfluoroalkyl group sulfonic acid and sulfonate carried by macromolecule and its preparation method and application |
CN101239999A (en) * | 2008-03-17 | 2008-08-13 | 江南大学 | Method for preparing alkylglycoside by using solid-carrying heteropolyacid catalyst |
EP2145895A1 (en) * | 2008-07-08 | 2010-01-20 | Commissariat à l'Energie Atomique | Process for the manufacturing of glycochips |
Non-Patent Citations (5)
Title |
---|
A. DE ANGELIS等: "Studies on supported triflic acid in alkylation", 《CATALYSIS TODAY》 * |
A. DE ANGELIS等: "Studies on supported triflic acid in alkylation", 《CATALYSIS TODAY》, vol. 65, 20 February 2001 (2001-02-20), XP027361277 * |
PEI NIAN LIU等: "Triflic acid adsorbed on silica gel as an efficient and recyclable catalyst for the addition of b-dicarbonyl compounds to alcohols and alkenes", 《GREEN CHEMISTRY》 * |
PEI NIAN LIU等: "Triflic acid adsorbed on silica gel as an efficient and recyclable catalyst for the addition of b-dicarbonyl compounds to alcohols and alkenes", 《GREEN CHEMISTRY》, vol. 12, 12 May 2010 (2010-05-12), pages 1049 - 1055 * |
武钦佩,李善茂: "《保护基化学》", 30 April 2007, 化学工业出版社 * |
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