CN113603730B - Method for selectively synthesizing oxyglycoside or 2-deoxysaccharide by using boric acid triester as saccharide acceptor - Google Patents
Method for selectively synthesizing oxyglycoside or 2-deoxysaccharide by using boric acid triester as saccharide acceptor Download PDFInfo
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Abstract
The invention provides a method for selectively synthesizing oxyglycoside or 2-deoxy sugar by taking boric acid triester as a sugar receptor, wherein 3, 4-O-galactose carbonic ester enase and boric acid triester are stirred and reacted in tetrahydrofuran solvent by taking palladium acetate as a catalyst and 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene as a ligand at room temperature to obtain the oxyglycoside; or, 3, 4-O-galactose carbonic ester enase and trimethyl borate are stirred and reacted in methylene dichloride solvent by taking copper trifluoromethane sulfonate as a catalyst at room temperature to obtain the 2-deoxy sugar. According to the technical scheme, the three-dimensional selective synthesis of 2, 3-unsaturated oxygen sugar and 2-deoxy sugar is realized by adopting the reaction of boric acid triester and an alkene sugar donor under mild conditions.
Description
Technical Field
The invention relates to a method for respectively realizing stereoselective synthesis of 2, 3-unsaturated oxygen sugar and 2-deoxy sugar by adopting boric acid triester to react with an olefine sugar donor under mild conditions, belonging to the technical field of organic synthesis.
Background
Sugar is another very important living substance other than protein and nucleic acid, and sugar and covalent compounds thereof play a very important role in life science and pharmaceutical research. Oxyglycosides are the most widely occurring glycoside types in nature, which are widely present in natural products, such as Salidroside (Salidroside) which can enhance immunity, inhibit tumor growth and have whitening and anti-radiation effects, gastrodin (Gastrodin) which can improve neurasthenia, sciatica, trigeminal neuralgia, etc. In addition, 2-deoxysaccharides are also carbohydrate backbones prevalent in biologically active natural products, and generally have antibacterial, anticancer or cardiotonic activity, such as Digitonin (Digitonin) and Digitoxin (Digitonin) obtained from leaves and seeds of purple flower digitalis. Because of the complex structure of the saccharide, the saccharide has a plurality of active hydroxyl groups and chiral centers, and the formed glycosidic bond has two three-dimensional structures of alpha and beta, the efficient three-dimensional selective construction of the glycosidic bond is one of bottleneck problems restricting the development of the sugar science. Glycosylation is one of the most important synthetic methods for the synthesis of glycosides and oligosaccharides associated with natural products and analogues thereof.
Classical glycosylation methods typically employ alcohols or phenolic compounds as sugar acceptors to react with saturated sugar donors/2-deoxy sugar donors to yield oxyglycosides or 2-deoxy sugars. The saturated sugar donor can realize the stereoselectivity construction of new glycosidic bonds through methods of ortho-group participation, anomeric effect, intramolecular glycosyl ligand transfer (IAD) and the like. Due to the difference in reactivity between phenols and ordinary alcohols, conventional glycosyl synthesis aryl glycosides often require large amounts of activators and substrates, and sometimes low temperature reaction conditions to prevent rearrangement of the O-glycoside to aryl C-glycoside. Furthermore, although acid and base promoted synthesis of 2-deoxy sugars is popular in the field of sugar chemistry, glycosylation reactions carried out by these methods are carried out at low or high temperatures, potentially yielding large amounts of unwanted hemi-acetal byproducts. Or by stereoselective assembly of the 2-deoxy sugar donor, temporary attachment of the directing group at the C2 position, but this approach is inefficient. The invention adopts the reaction of the boric acid triester and the alkene sugar donor under mild conditions to respectively realize the stereoselective synthesis of the 2, 3-unsaturated oxygen sugar and the 2-deoxy sugar.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for selectively synthesizing oxyglycoside or 2-deoxysugar by using boric acid triester as a sugar receptor, which comprises the following steps:
3, 4-O-galactose carbonic ester enase and boric acid triester are stirred and reacted in tetrahydrofuran solvent under the condition of taking palladium acetate as a catalyst and 4, 5-bis (diphenyl phosphine) -9, 9-dimethyl xanthene as a ligand at room temperature to obtain oxyglycoside;
in the synthesis, the coordination of palladium catalyst, phosphine ligand and allyl sugar takes place to carry out decarboxylation allylation reaction to form an allyl sugar-palladium catalyst complex, and the boric acid triester is taken as a terminal group of the attack sugar of a nucleophilic reagent to obtain the oxyglycoside.
Or, 3, 4-O-galactose carbonic ester enase and trimethyl borate are stirred and reacted in methylene dichloride solvent by taking copper trifluoromethane sulfonate as a catalyst at room temperature to obtain the 2-deoxy sugar.
In this synthesis, the double bond of the metal catalyst and the glycal is directly added without decarboxylation, and then the borate is used as a nucleophilic reagent to attack the terminal position of the sugar end, thus generating 2-deoxy sugar.
The molar ratio of the 3, 4-O-galactose carbonic ester allyl sugar and the boric acid triester is 1:1.2-2.0.
The said boric acid triester includes trimethyl borate, triethyl borate, tripropyl borate, etc., triphenyl borate, tricresyl borate, etc.
The 4, 5-bis (diphenyl phosphine) -9, 9-dimethyl xanthene ligand can also be 1, 4-bis (diphenyl phosphine) butane, and the addition amount of the ligand is 5-15% of the molar amount of 3, 4-O-galactose carbonate glycal.
The tetrahydrofuran solvent may also be toluene solvent, which is in excess relative to the starting materials.
The addition amount of the copper trifluoromethane sulfonate catalyst is 1-10% of the molar amount of the 3, 4-O-galactose carbonate alkene sugar.
The invention adopts the reaction of the boric acid triester and the alkene sugar donor under mild conditions to respectively realize the stereoselective synthesis of the 2, 3-unsaturated oxygen sugar and the 2-deoxy sugar. The specific process route is as follows:
results of the review experiments, the optimal reaction conditions for galactose 2, 3-unsaturated glycoxyglycoside were found to be in Pd (OAc) 2 As a catalyst, xantphos is used as a ligand, and THF is used as a solvent, so that the reaction effect is the best; the optimal reaction conditions for galactose 2-deoxyglycoxyglycoside are those in Cu (OTf) 2 The reaction was best when DCM was used as solvent as catalyst.
According to the technical scheme, beta-2, 3-unsaturated oxygen sugar can be obtained through metal coordination to form intermediate complex stereoselectivity; the stereoselectivity of 2-deoxy sugar is analyzed by adding metal triflate Lewis acid and allyl sugar, namely how the solvent, the catalyst and the ligand are selected.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of compound 12.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of compound 12.
FIG. 3 shows the nuclear magnetic resonance hydrogen spectrum of compound 33.
FIG. 4 is a nuclear magnetic resonance carbon spectrum of compound 33.
Detailed Description
Experimental reagent
Palladium acetate (Shanghai Mirelin technologies Co., ltd.), copper triflate (Shanghai Ala Di Biochemical Co., ltd.), petroleum ether (boiling range 60-90 ℃, jinan century reaching chemical Co., ltd.), ethyl acetate (analytically pure, shandong Xu Chen Hua Gong Co., ltd.), anhydrous sodium sulfate (analytically pure, shanghai Zea Biotechnology Co., ltd.), deuterated chloroform (deuterium atom content 99.8%, TMS content 0.03% V/V,10 x 0.5 ml/box, moleKULA Co., UK); nuclear magnetic resonance tube (5 mm 100/pk 2ST500-8, norell Co., U.S.A.).
Experimental instrument
ZXZ-4 rotary vane vacuum pump (Tanshi vacuum apparatus Co., ltd., lin-sea), DZF-6020 vacuum drying oven (Shanghai New Miao medical instruments Co., ltd.), SHB-IIIA circulating water type multipurpose vacuum pump (Shanghai Yukang scientific teaching Instrument Co., ltd.), CL-4 type flat magnetic stirrer (Zheng, great wall Co., ltd.), EYELA SB-1100 rotary evaporator (Shanghai Ailang instruments Co., ltd.), FA2104B analytical balance (Shanghai plain scientific instrument limited), XRC-1 micro-melting point tester (university of Sichuan instrumentation), DF-101S heat collection type constant temperature heating magnetic stirrer (consolidated quartz and quartz pre-bloom instrumentation), GZX-9240MBE digital display blast drying box (Shanghai bosin real company medical equipment factory), ZF-6 three-purpose ultraviolet analyzer (Shanghai jiaweng scientific limited), ultrashed 400MHz Plus nuclear magnetic resonance instrument (Bruker company of switzerland).
Example 1
Taking galactose carbonate alkene sugar as an example, adopting an optimized experimental scheme of different catalysts and ligands, and particularlyThe following are provided: palladium acetate (Pd (OAc) 2 1.1mg,0.005 mmol), 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene (Xantphos, 5.8mg,0.01 mmol), sugar acceptor (trimethyl borate) (0.15 mmol) was added 2mL tetrahydrofuran and 3, 4-O-galactose carbonate glycal 1 (0.1 mmol). Stirring at room temperature, TLC monitoring reaction progress, terminating reaction after complete disappearance of the alkene sugar, extracting and collecting organic phase, vacuum distilling to remove solvent to obtain crude product, and column chromatography with petroleum ether/ethyl acetate solution as mobile phase to obtain 4-hydroxy-2, 3-unsaturated oxygen glycoside (yield 88%). The spectrogram data is 1 H NMR(400MHz,CDCl 3 δ7.70–7.66(m,4H),7.48–7.37(m,6H),5.02–4.97(m,1H),4.88–4.80(m,2H),3.96(td,J＝6.7,1.7Hz,1H),3.89–3.79(m,2H),3.35(s,3H),2.45(ddd,J＝15.8,5.7,3.9Hz,1H),1.81(ddd,J＝15.8,6.7,3.4Hz,1H),1.06(s,9H).
13 C NMR(101MHz,CDCl 3 )δ154.3,135.6,135.5,133.1,132.8,129.9,129.9,127.9,127.8,96.3,73.4,72.1,67.9,61.7,55.2,29.4,26.8,19.2.
Screening synthesis of DPPB and DPPF ligands was performed under the conditions of the above examples, and the effects thereof were as in examples 1-1 and 1-2.
Pd (acac) was carried out separately on the condition of the process of the above example 2 、Pd(pph 3 ) 4 、Pd(pph 3 ) 4 ·Cl 2 The catalyst was synthesized by screening, and the effect thereof was as in examples 1-4, 1-5 and 1-6.
DCM and CH were performed respectively, subject to the process of the above examples 3 CN, toluene, and the like, and the implementation effects thereof are as in examples 1-7, 1-8 and 1-9.
Note that: b isolation yield
Example 2
Copper trifluoromethane sulfonate (Cu (OTf) 2 1.8mg,0.005 mmol), and sugar acceptor (trimethyl borate) (0.15 mmol) were added to 2mL of dichloromethane and 3,4-O-galactose carbonate alkene sugar 1 (0.1 mmol). Stirring at room temperature, TLC monitoring reaction progress, terminating reaction after complete disappearance of allyl raw material, extracting and collecting organic phase, vacuum distilling to remove solvent to obtain crude product, and performing column chromatography with petroleum ether/ethyl acetate solution as mobile phase to obtain 2-deoxysugar (yield 78%), wherein the spectrum data is 1 H NMR(400MHz,CDCl 3 )δ7.74–7.68(m,4H),7.47–7.36(m,6H),6.16(ddd,J＝10.0,5.1,1.5Hz,1H),5.85–5.79(m,1H),4.96(d,J＝1.5Hz,1H),4.05–3.95(m,2H),3.88(dd,J＝10.5,6.0Hz,1H),3.78–3.73(m,1H),3.48(s,3H),2.02(d,J＝9.7Hz,1H),1.07(s,9H).
13 C NMR(101MHz,CDCl 3 )δ135.6,133.4,133.3,131.0,130.7,129.8,129.7,127.8,127.7,98.8,75.6,63.3,62.5,55.8,26.8,19.3.
The process is as follows:
the screening synthesis of different catalysts of Hg (OTf) 2, ag (OTf), zn (OTf) 2, sc (OTf) 3, cu (OTf) 2 was carried out on the conditions of the above examples, and the effects thereof were as in examples 2-1, 2-2, 2-3, 2-4, 2-5.
The screening synthesis of different solvents of THF, CH3CN and Toluene was carried out under the conditions of the process of the above examples, and the implementation effects were as in examples 2-6, 2-7 and 2-8.
Note that a test uses 0.1mmol galactose carbonate alkene sugar and 0.15mmol trimethyl borate, 5mol% catalyst, 10mol% phosphine ligand in 2mL solvent at room temperature stirring reaction; b isolation yield; c using only catalyst without ligand added. XantPhos 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene, DPPB 1, 4-bis (diphenylphosphine) butane, DPPF 1,1' -bis (diphenylphosphine) ferrocene.
Examples 1 and 2 of the present inventionScreening optimization was performed. The catalyst and ligand were first screened under the condition of THF as a solvent (entries 1-6). Experimental results indicate that when Xantphos is used as ligand Pd (OAc) 2 When used as a catalyst, the yield of 12 can reach 82% (entry 3). Next, the solvent was optimized (entries 7-9), and the optimization result showed that the reaction was best with THF as the solvent, and the yield of 12 could reach 88% (entry 3). In order to be able to obtain 33, the present invention tried to change the catalyst type, whether or not highly efficient selective synthesis of 33 could be achieved (entries 10-17). The experimental results show that different results can be obtained in the presence of different trifluoromethane sulphonates, when Cu (OTf) is used 2 As catalyst, yields up to 78% were best (entry 14) followed by solvent optimization (entries 14-17), and the optimization results showed that the reaction was best with DCM as solvent.
Results of the review experiments, the optimal reaction conditions for galactose 2, 3-unsaturated glycoxyglycoside were found to be in Pd (OAc) 2 Xantphos as a ligand, CS as a catalyst 2 CO 3 As an additive, THF as a solvent gave the best reaction; the optimal reaction conditions for galactose 2-deoxyglycoxyglycoside are those in Cu (OTf) 2 The reaction was best when DCM was used as solvent as catalyst.
Under the condition of the route, the invention also prepares the alpha-methyl-2-deoxy sugar by taking the 3, 4-O-galactose carbonate alkene sugar as a raw material, and the technical route is as follows:
copper trifluoromethane sulfonate (Cu (OTf) 2 1.8mg,0.005 mmol), and sugar acceptor (trimethyl borate) (0.15 mmol) were added to 2mL of dichloromethane and 3, 4-O-galactose carbonate glycal 1 (0.1 mmol). Stirring at room temperature, monitoring the reaction progress by TLC, stopping the reaction after the alkene sugar material completely disappears, extracting and collecting an organic phase, decompressing and distilling to remove a solvent to obtain a crude product, and performing column chromatography by adopting petroleum ether/ethyl acetate solution as a mobile phase to obtain 2-deoxysugar [ ]Yield 78%).
Example 2
Palladium acetate (Pd (OAc) 2 1.1mg,0.005 mmol), 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene (Xantphos, 5.8mg,0.01 mmol), sugar acceptor (trimethyl borate) (0.15 mmol) was added 2mL tetrahydrofuran and 3, 4-O-galactose carbonate glycal 1 (0.1 mmol). Stirring at room temperature, TLC monitoring reaction progress, terminating reaction after complete disappearance of the alkene sugar, extracting and collecting organic phase, vacuum distilling to remove solvent to obtain crude product, and column chromatography with petroleum ether/ethyl acetate solution as mobile phase to obtain 4-hydroxy-2, 3-unsaturated oxygen glycoside (yield 88%).
Substrate range
The procedure was followed as in example 1, except that the borate triester was merely used as the corresponding sugar acceptor, to give the 2, 3-unsaturated oxyglycoside product and yield as follows:
the procedure was followed as in example 2, except that only the boric acid triester was modified as the corresponding sugar acceptor, to give the 2-deoxy sugar product and yield as follows:
Claims (4)
1. a method for selectively synthesizing 2-deoxy sugar by using boric acid triester as a sugar receptor, comprising the steps of:
3, 4-O-galactose carbonate alkene sugar and trimethyl borate are stirred and reacted in a dichloromethane solvent in the presence of copper trifluoromethane sulfonate as a catalyst, wherein the addition amount of the copper trifluoromethane sulfonate catalyst is 1-10% of the molar amount of the 3, 4-O-galactose carbonate alkene sugar, and the 2-deoxy sugar is obtained by stirring and reacting at room temperature.
2. The method for selectively synthesizing 2-deoxy sugar by using triester borate as a sugar acceptor according to claim 1, wherein the molar ratio of the allyl 3, 4-O-galactose carbonate to trimethyl borate is 1:1.2-2.0.
3. The method for selectively synthesizing 2-deoxy sugar with a tri-borate as claimed in claim 1, wherein the catalyst is AgOTf, hg (OTf) 2 Or Zn (OTf) 2 。
4. The method of claim 1, wherein the methylene chloride solvent is tetrahydrofuran or toluene, and the solvent is selected to provide a sugar donor concentration of between 0.1 and M and 10M.
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