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【结 构 式】 
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【分子编号】29907 【品名】(3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid 【CA登记号】138-59-0 |
【 分 子 式 】C7H10O5 【 分 子 量 】174.1534 【元素组成】C 48.28% H 5.79% O 45.93% |
合成路线1
该中间体在本合成路线中的序号：(XIV)2) The esterification of Shikimic acid (XIV) with MeOH/TsOH gives the methyl ester (XV), which is treated with 2,2-dimethoxypropane (II) and TsOH to yield the acetonide (XVI). The mesylation of (XVI) with mesyl chloride and TEA in dichloromethane gives the mesylated acetonide (XVII), which is hydrolyzed with HCl, yielding the dihydroxy ester (XVIII). The epoxidation of (XVIII) with DBU in THF affords the epoxide (XIX), which is protected with methyl chloromethyl ether to give compound (XX). The reaction of (XX) with sodium azide in refluxing methanol/water provides the hydroxy azide (XXI), which is acylated with mesyl chloride to the mesylate (XXII). The cyclization of (XXII) by means of triphenylphosphine in THF affords the aziridine (XXIII), which is treated with sodium azide in hot DMF to give the amino azide (XXIV). The deprotection of (XXIV) with HCl followed by tritylation of the free amino group with trityl chloride and TEA yields compound (XXV), which is cyclized by means of mesyl chloride and TEA to afford the tritylaziridine (XXVI). The cleavage of the aziridine ring of (XXVI) with 3-pentanol, followed by acetylation of the resulting amino group, affords the acetamido aziridine (XXVII), which is hydrolyzed at the ester group with KOH in THF/water to give the carboxylic acid (XXVIII). The esterification of (XXVIII) with ethanol, DCC and DMAP in dichloromethane affords the azido ester (XIII), which is finally reduced with triphenylphosphine in hot THF/water.
| 【1】 Castañer, J.; Leeson, P.A.; Graul, A.; Oseltamivir Phosphate. Drugs Fut 1999, 24, 11, 1189. |
| 【2】 Bischofberger, N.W.; Kim, C.U.; Lew, W.; Liu, H.; Williams, M.A. (Gilead Sciences Inc.); Novel selective inhibitors of viral or bacterial neuraminidases. EP 0759917; EP 0976734; JP 1999501908; WO 9626933 . |
| 【3】 Bischofberger, N.W.; Kim, C.U.; Williams, M.A.; Lew, W.; Liu, H. (Gilead Sciences Inc.); Carbocyclic cpds.. US 5763483 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 18319 | Chloro(methoxy)methane; Chloromethyl methyl ether | 107-30-2 | C2H5ClO | 详情 | 详情 | |
| (II) | 10722 | 1-Methoxy-1-methylethyl methyl ether; 2,2-Dimethoxypropane | 77-76-9 | C5H12O2 | 详情 | 详情 |
| (XIII) | 29906 | ethyl (3R,4R,5S)-4-(acetamido)-5-azido-3-(1-ethylpropoxy)-1-cyclohexene-1-carboxylate | C16H26N4O4 | 详情 | 详情 | |
| (XIV) | 29907 | (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid | 138-59-0 | C7H10O5 | 详情 | 详情 |
| (XV) | 29908 | methyl (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate | C8H12O5 | 详情 | 详情 | |
| (XVI) | 29909 | methyl (3aR,7R,7aS)-7-hydroxy-2,2-dimethyl-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C11H16O5 | 详情 | 详情 | |
| (XVII) | 29910 | methyl (3aR,7R,7aR)-2,2-dimethyl-7-[(methylsulfonyl)oxy]-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C12H18O7S | 详情 | 详情 | |
| (XVIII) | 29911 | methyl (3R,4R,5R)-3,4-dihydroxy-5-[(methylsulfonyl)oxy]-1-cyclohexene-1-carboxylate | C9H14O7S | 详情 | 详情 | |
| (XIX) | 29912 | methyl (1S,5R,6R)-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C8H10O4 | 详情 | 详情 | |
| (XX) | 29913 | methyl (1S,5R,6S)-5-(methoxymethoxy)-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C10H14O5 | 详情 | 详情 | |
| (XXI) | 29914 | methyl (3R,4S,5R)-5-azido-4-hydroxy-3-(methoxymethoxy)-1-cyclohexene-1-carboxylate | C10H15N3O5 | 详情 | 详情 | |
| (XXII) | 29915 | methyl (3R,4S,5R)-5-azido-3-(methoxymethoxy)-4-[(methylsulfonyl)oxy]-1-cyclohexene-1-carboxylate | C11H17N3O7S | 详情 | 详情 | |
| (XXIII) | 29916 | methyl (1R,5R,6R)-5-(methoxymethoxy)-7-azabicyclo[4.1.0]hept-3-ene-3-carboxylate | C10H15NO4 | 详情 | 详情 | |
| (XXIV) | 29917 | methyl (3R,4R,5S)-4-amino-5-azido-3-(methoxymethoxy)-1-cyclohexene-1-carboxylate | C10H16N4O4 | 详情 | 详情 | |
| (XXV) | 29918 | methyl (3R,4R,5S)-5-azido-3-hydroxy-4-(tritylamino)-1-cyclohexene-1-carboxylate | C27H26N4O3 | 详情 | 详情 | |
| (XXVI) | 29919 | methyl (1S,5S,6S)-5-azido-7-trityl-7-azabicyclo[4.1.0]hept-2-ene-3-carboxylate | C27H24N4O2 | 详情 | 详情 | |
| (XXVII) | 29920 | methyl (3R,4R,5S)-4-(acetamido)-5-azido-3-(1-ethylpropoxy)-1-cyclohexene-1-carboxylate | C15H24N4O4 | 详情 | 详情 | |
| (XXVIII) | 29921 | (3R,4R,5S)-4-(acetamido)-5-azido-3-(1-ethylpropoxy)-1-cyclohexene-1-carboxylic acid | C14H22N4O4 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XIV)The enzymatic resolution of the tricyclic carboxylate (XXIX) with chiralzyme L-2 and vinyl acetate gives the monoacetate (XXX) and the dihydroxy compound (XXXI) that are easily separated. The monosilylation of the less hindered OH group of (XXXI) with TBDMS-Cl and imidazole in DMF gives the monosilylated compound (XXXII), which is acylated with acetyl chloride, TEA and DMAP in dichloromethane yielding the monoacetate (XXXIII). The desilylation of (XXXIII) with TBAF in THF affords the secondary alcohol (XXXIV), which is oxidized with ammonium formate and PdCl2(PPh3)2 in acetonitrile to give the unsaturated ketone (XXXV). The epoxidation of the double bond of (XXXV) with H2O2 and Triton B in THF yields the ketoepoxide (XXXVI), which is reduced with NaBH4 in methanol to the epoxy alcohol (XXXVII). The esterification of (XXXVII) with benzoyl chloride affords the benzoate (XXXVIII), which is submitted to thermolysis at 300 C in diphenyl ether to provide the cyclohexenecarboxylate (XXXIX).The reaction of (XXXIX) with BF3 ethearate in toluene gives, through the nonisolable oxonium intermediate (XL), the monobenzoate (XLI), which is debenzoylated with K2CO3 in methanol to provide the methyl ester (XLII) of the target compound. Finally, this compound is hydrolyzed with KOH in THF.
| 【1】 Yoshida, N.; Ogasawara, K.; An enatioconvergent route to (-)-shikimic acid via a palladium-mediated elimination reaction. Org Lett 2000, 2, 10, 1461. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXIX),(XXXI) | 36851 | methyl (2R,3R,6S)-3,6-dihydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C13H16O4 | 详情 | 详情 | |
| (XIV) | 29907 | (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid | 138-59-0 | C7H10O5 | 详情 | 详情 |
| (XXX) | 36852 | methyl (2S,3S,6R)-6-(acetoxy)-3-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C15H18O5 | 详情 | 详情 | |
| (XXXII) | 36853 | methyl (2R,3R,6S)-6-[[tert-butyl(dimethyl)silyl]oxy]-3-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C19H30O4Si | 详情 | 详情 | |
| (XXXIII) | 36854 | methyl (2R,3R,6S)-3-(acetoxy)-6-[[tert-butyl(dimethyl)silyl]oxy]tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C21H32O5Si | 详情 | 详情 | |
| (XXXIV) | 36855 | methyl (2R,3R,6S)-3-(acetoxy)-6-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C15H18O5 | 详情 | 详情 | |
| (XXXV) | 36856 | methyl (2R)-6-oxotricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C13H14O3 | 详情 | 详情 | |
| (XXXVI) | 36857 | methyl (2R,4R,6R)-7-oxo-5-oxatetracyclo[7.2.1.0(2,8).0(4,6)]dodec-10-ene-2-carboxylate | C13H14O4 | 详情 | 详情 | |
| (XXXVII) | 36858 | methyl (2R,4R,6S,7R)-7-hydroxy-5-oxatetracyclo[7.2.1.0(2,8).0(4,6)]dodec-10-ene-2-carboxylate | C13H16O4 | 详情 | 详情 | |
| (XXXVIII) | 36859 | methyl (2R,4R,6R,7R)-7-(benzoyloxy)-5-oxatetracyclo[7.2.1.0(2,8).0(4,6)]dodec-10-ene-2-carboxylate | C20H20O5 | 详情 | 详情 | |
| (XXXIX) | 36860 | methyl (1R,5R,6R)-5-(benzoyloxy)-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C15H14O5 | 详情 | 详情 | |
| (XL) | 36861 | C15H14BF3O5 | 详情 | 详情 | ||
| (XLI) | 36862 | (1R,5R,6S)-5,6-dihydroxy-3-(methoxycarbonyl)-2-cyclohexen-1-yl benzoate | C15H16O6 | 详情 | 详情 | |
| (XLII) | 29908 | methyl (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate | C8H12O5 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(XIV)The enzymatic resolution of the tricyclic carboxylate (XXIX) with chiralzyme L-2 and vinyl acetate gives the monoacetate (XXX) and the dihydroxy compound (XXXI) that are easily separated. The hydrolysis of the acetate (XXX) with K2CO3 in methanol yields the diol (XLIII), which silylated with TBDMS-Cl and imidazole at the less hindered OH affording the silyl ether (XLIV). The acetylation of (XLIV) with acetyl chloride, TEA and DMAP gives the acetate (XLV), which is desilylated with TBAF in THF yielding the alcohol (XLVI). The oxidation of (XLVI) with ammonium formate and PdCl2(PPh3)2 in refluxing acetonitrile affords the ketone (XLVII), which is epoxidized with H2O2 and Triton B in THF providing the ketoepoxide (XLVIII). The thermolysis of (XLVIII) at 300 C in diphenyl ether gives the epoxycyclohexenone (II), which is reduced with NaBH4 and CeCl3 in methanol yielding a mixture of the two diastereomeric alcohols (L) and (LI) that are separated by column chromatography. The desired alcohol (LI) is treated with refluxing 80% AcOH to afford the methyl ester (XLII) of the target compound. Finally, this compound is hydrolyzed with KOH in THF. The undesired diastereomeric alcohol (L) is recycled to epoxyketone (II) by oxidation with tetrapropylammonium perruthenate (TPAP) and NMMO.
| 【1】 Yoshida, N.; Ogasawara, K.; An enatioconvergent route to (-)-shikimic acid via a palladium-mediated elimination reaction. Org Lett 2000, 2, 10, 1461. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXIX),(XXXI) | 36851 | methyl (2R,3R,6S)-3,6-dihydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C13H16O4 | 详情 | 详情 | |
| (IL) | 36865 | methyl (1S,6S)-5-oxo-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C8H8O4 | 详情 | 详情 | |
| (XIV) | 29907 | (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid | 138-59-0 | C7H10O5 | 详情 | 详情 |
| (XXX) | 36852 | methyl (2S,3S,6R)-6-(acetoxy)-3-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C15H18O5 | 详情 | 详情 | |
| (XLII) | 29908 | methyl (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate | C8H12O5 | 详情 | 详情 | |
| (XLIII) | 36867 | methyl (2S,3S,6R)-3,6-dihydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C13H16O4 | 详情 | 详情 | |
| (XLIV) | 36868 | methyl (2S,3S,6R)-6-[[tert-butyl(dimethyl)silyl]oxy]-3-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C19H30O4Si | 详情 | 详情 | |
| (XLV) | 36869 | methyl (2S,3S,6R)-3-(acetoxy)-6-[[tert-butyl(dimethyl)silyl]oxy]tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C21H32O5Si | 详情 | 详情 | |
| (XLVI) | 36870 | methyl (2S,3S,6R)-3-(acetoxy)-6-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C15H18O5 | 详情 | 详情 | |
| (XLVII) | 36863 | methyl (2S,3S)-3-(acetoxy)-6-oxotricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate | C15H16O5 | 详情 | 详情 | |
| (XLVIII) | 36864 | methyl (2S,3R,4R,6S)-3-(acetoxy)-7-oxo-5-oxatetracyclo[7.2.1.0(2,8).0(4,6)]dodec-10-ene-2-carboxylate | C15H16O6 | 详情 | 详情 | |
| (L) | 36866 | methyl (1S,5S,6R)-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C8H10O4 | 详情 | 详情 | |
| (LI) | 29912 | methyl (1S,5R,6R)-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C8H10O4 | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(I)A new industrial synthesis of (3R,4S,5S)-4,5-epoxy-3-(1-ethylpropoxy)-1-cyclohexene-1-carboxylic acid ethyl ester, a key intermediate in the synthesis of the oseltamivir phosphate has been developed: The esterification of (-)-shikimic acid (I) with SOCl2 and ethanol gives the expected ethyl ester (II), which is treated with 2,2-dimethoxypropane and p-toluenesulfonic acid in ethyl acetate to yield the acetonide (III). Mesylation of (III) with mesyl chloride and triethylamine in ethyl acetate affords mesylate (IV), which is trans-ketalized with 3-pentanone and trifluoromethanesulfonic acid giving the pentylidene ketal (V). Reductive opening of the ketal ring of (V) with triethylsilane and TiCl4 in dichloromethane gives the hydroxyether (VI), which is converted into the target epoxide by a treatment with NaHCO3 in ethanol/water. Another route to pentylidene ketal (V) has also been developed: The direct ketalization of ester (II) with 3-pentanone and trifluoromethanesulfonic acid gives the pentylidene ketal (VIII), which is then mesylated with mesyl chloride and triethylamine as before yielding the alredy described mesylate (V). From the above two routes, the route through the mesylate (IV) is preferred even though it is one step longer. Compound (IV) is a highly crystalline compound which can be purified efficiently. In contrast, intermediates (VIII) and (V) are oils and cannot be purified easily and often, the resulting epoxide (VII) obtained through pentylidene ketal (VIII) do not meet the quality requirements and may be reprocessed.
| 【1】 Fischer, R.; Henning, M.; Federspiel, M.; et al.; Industrial synthesis of the key precursor in the synthesis of the anti-influenza drug oseltamivir phosphate (Ro 64-0796/002, GS-4104-02): Ethyl (3R,4S,5S)-4,5-epoxy-3-(1-ethyl-propoxy)-cyclohex-1-ene-1-carboxylate. Org Process Res Dev 1999, 3, 4, 266. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 29907 | (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid | 138-59-0 | C7H10O5 | 详情 | 详情 |
| (II) | 41701 | ethyl (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate | C9H14O5 | 详情 | 详情 | |
| (III) | 41702 | ethyl (3aR,7R,7aS)-7-hydroxy-2,2-dimethyl-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C12H18O5 | 详情 | 详情 | |
| (IV) | 29899 | ethyl (3aR,7R,7aR)-2,2-dimethyl-7-[(methylsulfonyl)oxy]-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C13H20O7S | 详情 | 详情 | |
| (V) | 29900 | ethyl (3aR,7R,7aR)-2,2-diethyl-7-[(methylsulfonyl)oxy]-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C15H24O7S | 详情 | 详情 | |
| (VI) | 29901 | ethyl (3R,4R,5R)-3-(1-ethylpropoxy)-4-hydroxy-5-[(methylsulfonyl)oxy]-1-cyclohexene-1-carboxylate | C15H26O7S | 详情 | 详情 | |
| (VII) | 29902 | ethyl (1S,5R,6S)-5-(1-ethylpropoxy)-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate | C14H22O4 | 详情 | 详情 | |
| (VIII) | 41703 | ethyl (3aR,7R,7aS)-2,2-diethyl-7-hydroxy-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C14H22O5 | 详情 | 详情 |
合成路线5
该中间体在本合成路线中的序号：(XVI)The acceptor alcohol (XII) is synthesized by esterification of shikimic acid (XVI) with MeOH in the presence of H2SO4 to give methyl shikimate (XVII), which is then protected as the 3,4-acetonide (XIX) by transketalization with 2,2-dimethoxypropane (XVIII) by means of TsOH in acetonitrile. Hydrogenation of compound (XIX) over PtO2/C in MeOH affords the saturated ester (XX), which by acetylation with Ac2O in the presence of pyridine and DMAP in CH2Cl2 affords acetate (XXI). Deprotection of compound (XXI) by means of 80% aqueous AcOH at 80 °C provides diol (XXII), which is regioselectively converted to tosylate (XXIII) with TsCl in pyridine. Substitution of tosylate (XXIII) with NaN3 in DMF at 80 °C yields the corresponding azide (XXIV), which is then condensed with thioglycoside (XXV) by means of Br2 and Et4NBr in CH2Cl2/DMF/cyclohexene to obtain ether (XXVI). Finally, intermediate (XXVI) is submitted to deacetylation and simultaneous epimerization by means of NaOMe in MeOH, followed by reesterification with CH2N2 in Et2O .
| 【1】 Magnani, J.L., Patton, J.T. Jr., Sarkar, A.K., Svarovsky, S.A., Ernst, B. (GlycoMimetics, Inc.). Heterobifunctional pan-selectin inhibitors. EP 1934236, EP 2264043, JP 2009507031, US 2007054870, US 7728117, WO 2007028050. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XII) | 68493 | (1S,3S,4R,5R)-methyl 3-azido-5-hydroxy-4-(((2S,3S,4R,5S,6R)-3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yl)oxy)cyclohexanecarboxylate | C35H41N3O8 | 详情 | 详情 | |
| (XVI) | 29907 | (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid | 138-59-0 | C7H10O5 | 详情 | 详情 |
| (XVII) | 29908 | methyl (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate | C8H12O5 | 详情 | 详情 | |
| (XVIII) | 10722 | 1-Methoxy-1-methylethyl methyl ether; 2,2-Dimethoxypropane | 77-76-9 | C5H12O2 | 详情 | 详情 |
| (XIX) | 29909 | methyl (3aR,7R,7aS)-7-hydroxy-2,2-dimethyl-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate | C11H16O5 | 详情 | 详情 | |
| (XX) | 68500 | (3aS,7S,7aS)-methyl 7-hydroxy-2,2-dimethylhexahydrobenzo[d][1,3]dioxole-5-carboxylate | C11H18O5 | 详情 | 详情 | |
| (XXI) | 68499 | (3aS,7S,7aS)-methyl 7-acetoxy-2,2-dimethylhexahydrobenzo[d][1,3]dioxole-5-carboxylate | C13H20O6 | 详情 | 详情 | |
| (XXII) | 68498 | (3R,4S,5S)-methyl 3-acetoxy-4,5-dihydroxycyclohexanecarboxylate | C10H16O6 | 详情 | 详情 | |
| (XXIII) | 68497 | (3R,4S,5S)-methyl 3-acetoxy-4-hydroxy-5-(tosyloxy)cyclohexanecarboxylate | C17H22O8S | 详情 | 详情 | |
| (XXIV) | 68496 | (3R,4S,5R)-methyl 3-acetoxy-5-azido-4-hydroxycyclohexanecarboxylate | C10H15N3O5 | 详情 | 详情 | |
| (XXV) | 68502 | (3S,4S,5S,6R)-3,4,5-tris(benzyloxy)-2-(ethylthio)-6-methyltetrahydro-2H-pyran | C29H34O4S | 详情 | 详情 | |
| (XXVI) | 68501 | (3S,4S,5R)-methyl 3-acetoxy-5-azido-4-(((2R,3S,4S,5S,6R)-3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yl)oxy)cyclohexanecarboxylate | C37H43N3O9 | 详情 | 详情 |