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【结 构 式】 
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【分子编号】37071 【品名】ethyl 2-(triphenylphosphoranylidene)propanoate 【CA登记号】5717-37-3 |
【 分 子 式 】C23H23O2P 【 分 子 量 】362.408182 【元素组成】C 76.23% H 6.4% O 8.83% P 8.55% |
合成路线1
该中间体在本合成路线中的序号：(V)The reaction of 3-chloromethylpyridine (I) with the Grignard reagent of 4-bromobenzaldehyde diethylacetal (II) in THF gives 4-(3-pyridylmethyl)benzaldehyde diethylacetal (III), which is hydrolyzed with aqueous 1N HCl to 4-(3-pyridylmethyl)benzaldehyde (IV). The Wittig condensation of (IV) with 1-(ethoxycarbonyl)ethylidenetriphenylphosphorane (V) in CHCl3 affords 3-[4-(3-pyridylmethyl)phenyl]-2-methylacryl ic acid ethyl ester (VI), which is finally hydrolyzed with aqueous NaOH.
| 【1】 Tanouchi, T.; et al.; Pyridine derivatives. DE 2951786; FR 2445319; FR 2510108; GB 2039903; US 4271170; US 4317828 . |
| 【2】 Hillier, K.; Serradell, M.N.; Blancafort, P.; Castaner, J.; OKY-1581. Drugs Fut 1982, 7, 6, 399. |
| 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) | 15793 | 3-(Chloromethyl)pyridine | 3099-31-8 | C6H6ClN | 详情 | 详情 |
| (II) | 23171 | bromo[4-(diethoxymethyl)phenyl]magnesium | C11H15BrMgO2 | 详情 | 详情 | |
| (III) | 37069 | 3-[4-(diethoxymethyl)benzyl]pyridine; ethoxy[4-(3-pyridinylmethyl)phenyl]methyl ethyl ether | C17H21NO2 | 详情 | 详情 | |
| (IV) | 37070 | 4-(3-pyridinylmethyl)benzaldehyde | C13H11NO | 详情 | 详情 | |
| (V) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (VI) | 37072 | ethyl (E)-2-methyl-3-[4-(3-pyridinylmethyl)phenyl]-2-propenoate | C18H19NO2 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(X)The enantioselective condensation of 3-(trimethylsilyl)propynal (V) with allylmagnesium bromide (VI) by means of (+)-Ipc2B-OMe as chiral catalyst gives hex-5-en-1-yn-3(R)-ol (VII), which is silylated with Tbdps-Cl and imidazole to yield the silyl ether (VIII). The oxidation of the terminal double bond of (VII) by means of OsO4 and NaIO4 affords the aldehyde (IX), which is submitted to a Wittig condensation with the phosphorane (X) in benzene to provide the unsaturated ester (XI). The enantioselective dihydroxylation of the double bond of (XI) with AD-mix-beta in tert-butanol/water gives the dihydroxyester (XII), which is protected with 2-methoxypropene (XIII) and PPTS to yield the isopropylidene ketal (XIV). The bromination of the triple bond of (XIV), followed by selective hydrogenation, affords the cis-bromovinyl compound (XV), whose ester group is reduced with LiAlH4 in THF to provide the primary alcohol (XVI). The oxidation of (XVI) with (COCl)2 and TEA in DMSO gives the carbaldehyde (XVII), which is submitted to a Wittig condensation with the phosphorane (XVIII) in hot dichloromethane to yield the diunsaturated aldehyde (XIX). The enantioselective condensation of aldehyde (XIX) with allylmagnesium bromide catalyzed by (+)Ipc2-B-OMe affords the chiral alcohol (XX), which is esterified with acryloyl chloride (XXI) and DIEA in dichloromethane to provide the ester (XXII). Compound (XXII) is submitted to a ring-closing metathesis catalyzed by a Rh catalyst (Grubbs's catalyst), yielding the dihydropyran derivative (XXIII), which is submitted to cleavage of the acetonide group by means of Montmorillonite K 10 to afford the diol (XXIV). The condensation of the bromovinyl group of (XXIV) with the intermediate boronic ester (IV) by means of Pd(PPh3)4 and Ag2O gives compound (XXV) with the complete backbone of the target fostriecin. The selective monosilylation of (XXV) with Tbdps-OTf gives the intermediate (XXVI).
| 【1】 Falck, J.R.; Reddy, Y.K.; Asymmetric total synthesis of (+)-fostriecin. Org Lett 2002, 4, 6, 969. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 55458 | tert-butyl(diphenyl){[(2E,4Z)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,4-pentadienyl]oxy}silane; tert-butyl(diphenyl)silyl (2E,4Z)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,4-pentadienyl ether | C27H37BO3Si | 详情 | 详情 | |
| (V) | 20043 | 3-(trimethylsilyl)-2-propynal | C6H10OSi | 详情 | 详情 | |
| (VI) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (VII) | 55459 | (3R)-5-hexen-1-yn-3-ol | C6H8O | 详情 | 详情 | |
| (VIII) | 55460 | tert-butyl(diphenyl)silyl (1R)-1-ethynyl-3-butenyl ether; tert-butyl{[(1R)-1-ethynyl-3-butenyl]oxy}diphenylsilane | C22H26OSi | 详情 | 详情 | |
| (IX) | 55461 | (3R)-3-{[tert-butyl(diphenyl)silyl]oxy}-4-pentynal | C21H24O2Si | 详情 | 详情 | |
| (X) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XI) | 55462 | ethyl (E,5R)-5-{[tert-butyl(diphenyl)silyl]oxy}-2-methyl-2-hepten-6-ynoate | C26H32O3Si | 详情 | 详情 | |
| (XII) | 55463 | ethyl (2S,3R,5R)-5-{[tert-butyl(diphenyl)silyl]oxy}-2,3-dihydroxy-2-methyl-6-heptynoate | C26H34O5Si | 详情 | 详情 | |
| (XIII) | 17354 | isopropenyl methyl ether; 2-methoxy-1-propene | 116-11-0 | C4H8O | 详情 | 详情 |
| (XIV) | 55464 | ethyl (4S,5R)-5-((2R)-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butynyl)-2,2,4-trimethyl-1,3-dioxolane-4-carboxylate | C29H38O5Si | 详情 | 详情 | |
| (XV) | 55465 | ethyl (4S,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolane-4-carboxylate | C29H39BrO5Si | 详情 | 详情 | |
| (XVI) | 55466 | [(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]methanol | C27H37BrO4Si | 详情 | 详情 | |
| (XVII) | 55467 | (4S,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolane-4-carbaldehyde | C27H35BrO4Si | 详情 | 详情 | |
| (XVIII) | 55468 | 2-(triphenylphosphoranylidene)acetaldehyde | C20H17OP | 详情 | 详情 | |
| (XIX) | 55469 | (E)-3-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]-2-propenal | C29H37BrO4Si | 详情 | 详情 | |
| (XX) | 55470 | (1E,3R)-1-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]-1,5-hexadien-3-ol | C32H43BrO4Si | 详情 | 详情 | |
| (XXI) | 11577 | Acryloyl chloride; Acrylyl chloride;2-Propenoyl chloride | 814-68-6 | C3H3ClO | 详情 | 详情 |
| (XXII) | 55471 | (1R)-1-{(E)-2-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]ethenyl}-3-butenyl acrylate | C35H45BrO5Si | 详情 | 详情 | |
| (XXIII) | 55472 | (6R)-6-{(E)-2-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]ethenyl}-5,6-dihydro-2H-pyran-2-one | C33H41BrO5Si | 详情 | 详情 | |
| (XXIV) | 55473 | (6R)-6-((1E,3R,4R,6R,7Z)-8-bromo-6-{[tert-butyl(diphenyl)silyl]oxy}-3,4-dihydroxy-3-methyl-1,7-octadienyl)-5,6-dihydro-2H-pyran-2-one | C30H37BrO5Si | 详情 | 详情 | |
| (XXV) | 55474 | (6R)-6-((1E,3R,4R,6R,7Z,9Z,11E)-6,13-bis{[tert-butyl(diphenyl)silyl]oxy}-3,4-dihydroxy-3-methyl-1,7,9,11-tridecatetraenyl)-5,6-dihydro-2H-pyran-2-one | C51H62O6Si2 | 详情 | 详情 | |
| (XXVI) | 55475 | (6R)-6-((1E,3R,4R,6R,7Z,9Z,11E)-3,6,13-tris{[tert-butyl(diphenyl)silyl]oxy}-4-hydroxy-3-methyl-1,7,9,11-tridecatetraenyl)-5,6-dihydro-2H-pyran-2-one | C67H80O6Si3 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(XXIV)Assembly of the target compound: The protection of the lactone (XXI) with benzyl trichloroacetimidate gives the benzyl ether (XXII), which is reduced with DIBAL in toluene to yield the lactol (XXIII). The reaction of (XXIII) with phosphorane (XXIV) in refluxing benzene affords the hydroxy-heptenoic ester (XXV), which is treated with Tbdms-Cl and imidazole to provide the silyl ether (XXVI). The reduction of the ester group of (XXVI) with DIBAL in dichloromethane furnishes the allylic alcohol (XXVII), which by a Sharpless asymmetric epoxidation gives the epoxyalcohol (XXVIII). The oxidation of the OH group of (XXVIII) with SO3/pyridine complex yields the epoxyaldehyde (XXIX), which by reaction with tetrabromomethane, PPh3 and TEA in dichloromethane affords the dibromovinyl derivative (XXX). The reaction of (XXX) with TBAF in THF provides the bromoacetylenic compound (XXXI), which is cyclized by means of BF3/Et2O complex in dichloromethane, furnishing the acetylenic tetrahydropyran (XXXII). The reaction of (XXXII) with Tes-Cl and imidazole in DMF gives the silyl ether (XXXIII), which is condensed with the intermediate carbaldehyde (IV) by means of CrCl2 in DMF to yield the propargyl alcohol (XXXIV). The oxidation of the OH group of (XXXIV) with MnO2 affords the corresponding ketone (XXXV), which is hydrogenated and deprotected with H2 over Pd/C in methanol to provide the saturated dihydroxyketone (XXXVI).
| 【1】 Forsyth, G.J.; Gonzalez, I.C.; Total synthesis of tryrsiferyl 23-acetate, a specific inhibitor of protein phosphatase 2A and anti-leukemic inducer of apoptosis. J Am Chem Soc 2000, 122, 38, 9099. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 40660 | CH5AlClN | 详情 | 详情 | ||
| (XXI) | 46090 | (5R)-5-(hydroxymethyl)dihydro-2(3H)-furanone | C5H8O3 | 详情 | 详情 | |
| (XXII) | 46076 | (5R)-5-[(benzyloxy)methyl]dihydro-2(3H)-furanone | C12H14O3 | 详情 | 详情 | |
| (XXIII) | 46077 | (5R)-5-[(benzyloxy)methyl]tetrahydro-2-furanol | C12H16O3 | 详情 | 详情 | |
| (XXIV) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XXV) | 46078 | ethyl (E,6R)-7-(benzyloxy)-6-hydroxy-2-methyl-2-heptenoate | C17H24O4 | 详情 | 详情 | |
| (XXVI) | 46079 | ethyl (E,6R)-7-(benzyloxy)-6-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-2-heptenoate | C23H38O4Si | 详情 | 详情 | |
| (XXVII) | 46080 | (E,6R)-7-(benzyloxy)-6-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-2-hepten-1-ol | C21H36O3Si | 详情 | 详情 | |
| (XXVIII) | 46081 | [(2R,3R)-3-((3R)-4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]butyl)-2-methyloxiranyl]methanol | C21H36O4Si | 详情 | 详情 | |
| (XXIX) | 46082 | (2S,3R)-3-((3R)-4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]butyl)-2-methyl-2-oxiranecarbaldehyde | C21H34O4Si | 详情 | 详情 | |
| (XXX) | 46083 | benzyl (2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-4-[(2R,3R)-3-(2,2-dibromovinyl)-3-methyloxiranyl]butyl ether; ([(1R)-1-[(benzyloxy)methyl]-3-[(2R,3R)-3-(2,2-dibromovinyl)-3-methyloxiranyl]propyl]oxy)(tert-butyl)dimethylsilane | C22H34Br2O3Si | 详情 | 详情 | |
| (XXXI) | 46084 | (2R)-1-(benzyloxy)-4-[(2R,3R)-3-(2-bromoethynyl)-3-methyloxiranyl]-2-butanol | C16H19BrO3 | 详情 | 详情 | |
| (XXXII) | 46085 | (2S,3R,6R)-6-[(benzyloxy)methyl]-2-(2-bromoethynyl)-2-methyltetrahydro-2H-pyran-3-ol | C16H19BrO3 | 详情 | 详情 | |
| (XXXIII) | 46086 | [[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-(2-bromoethynyl)-2-methyltetrahydro-2H-pyran-3-yl]oxy](triethyl)silane; benzyl [(2R,5R,6S)-6-(2-bromoethynyl)-6-methyl-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]methyl ether | C22H33BrO3Si | 详情 | 详情 | |
| (XXXIV) | 46087 | 3-[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-methyl-3-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-2-propyn-1-ol | C31H49BrO5Si | 详情 | 详情 | |
| (XXXV) | 46088 | 3-[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-methyl-3-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-2-propyn-1-one | C31H47BrO5Si | 详情 | 详情 | |
| (XXXVI) | 46089 | 1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-3-[(2S,3R,6R)-3-hydroxy-6-(hydroxymethyl)-2-methyltetrahydro-2H-pyran-2-yl]-1-propanone | C18H31BrO5 | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(XXIV)Assembly of the target compound: The protection of the lactone (XXI) with benzyl trichloroacetimidate gives the benzyl ether (XXII), which is reduced with DIBAL in toluene to yield the lactol (XXIII). The reaction of (XXIII) with phosphorane (XXIV) in refluxing benzene affords the hydroxy-heptenoic ester (XXV), which is treated with Tbdms-Cl and imidazole to provide the silyl ether (XXVI). The reduction of the ester group of (XXVI) with DIBAL in dichloromethane furnishes the allylic alcohol (XXVII), which by a Sharpless asymmetric epoxidation gives the epoxyalcohol (XXVIII). The oxidation of the OH group of (XXVIII) with SO3/pyridine complex yields the epoxyaldehyde (XXIX), which by reaction with tetrabromomethane, PPh3 and TEA in dichloromethane affords the dibromovinyl derivative (XXX). The reaction of (XXX) with TBAF in THF provides the bromoacetylenic compound (XXXI), which is cyclized by means of BF3/Et2O complex in dichloromethane, furnishing the acetylenic tetrahydropyran (XXXII). The reaction of (XXXII) with Tes-Cl and imidazole in DMF gives the silyl ether (XXXIII), which is condensed with the intermediate carbaldehyde (IV) by means of CrCl2 in DMF to yield the propargyl alcohol (XXXIV). The oxidation of the OH group of (XXXIV) with MnO2 affords the corresponding ketone (XXXV), which is hydrogenated and deprotected with H2 over Pd/C in methanol to provide the saturated dihydroxyketone (XXXVI).
| 【1】 Forsyth, G.J.; Gonzalez, I.C.; Total synthesis of tryrsiferyl 23-acetate, a specific inhibitor of protein phosphatase 2A and anti-leukemic inducer of apoptosis. J Am Chem Soc 2000, 122, 38, 9099. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 40660 | CH5AlClN | 详情 | 详情 | ||
| (XXI) | 46090 | (5R)-5-(hydroxymethyl)dihydro-2(3H)-furanone | C5H8O3 | 详情 | 详情 | |
| (XXII) | 46076 | (5R)-5-[(benzyloxy)methyl]dihydro-2(3H)-furanone | C12H14O3 | 详情 | 详情 | |
| (XXIII) | 46077 | (5R)-5-[(benzyloxy)methyl]tetrahydro-2-furanol | C12H16O3 | 详情 | 详情 | |
| (XXIV) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XXV) | 46078 | ethyl (E,6R)-7-(benzyloxy)-6-hydroxy-2-methyl-2-heptenoate | C17H24O4 | 详情 | 详情 | |
| (XXVI) | 46079 | ethyl (E,6R)-7-(benzyloxy)-6-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-2-heptenoate | C23H38O4Si | 详情 | 详情 | |
| (XXVII) | 46080 | (E,6R)-7-(benzyloxy)-6-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-2-hepten-1-ol | C21H36O3Si | 详情 | 详情 | |
| (XXVIII) | 46081 | [(2R,3R)-3-((3R)-4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]butyl)-2-methyloxiranyl]methanol | C21H36O4Si | 详情 | 详情 | |
| (XXIX) | 46082 | (2S,3R)-3-((3R)-4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]butyl)-2-methyl-2-oxiranecarbaldehyde | C21H34O4Si | 详情 | 详情 | |
| (XXX) | 46083 | benzyl (2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-4-[(2R,3R)-3-(2,2-dibromovinyl)-3-methyloxiranyl]butyl ether; ([(1R)-1-[(benzyloxy)methyl]-3-[(2R,3R)-3-(2,2-dibromovinyl)-3-methyloxiranyl]propyl]oxy)(tert-butyl)dimethylsilane | C22H34Br2O3Si | 详情 | 详情 | |
| (XXXI) | 46084 | (2R)-1-(benzyloxy)-4-[(2R,3R)-3-(2-bromoethynyl)-3-methyloxiranyl]-2-butanol | C16H19BrO3 | 详情 | 详情 | |
| (XXXII) | 46085 | (2S,3R,6R)-6-[(benzyloxy)methyl]-2-(2-bromoethynyl)-2-methyltetrahydro-2H-pyran-3-ol | C16H19BrO3 | 详情 | 详情 | |
| (XXXIII) | 46086 | [[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-(2-bromoethynyl)-2-methyltetrahydro-2H-pyran-3-yl]oxy](triethyl)silane; benzyl [(2R,5R,6S)-6-(2-bromoethynyl)-6-methyl-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]methyl ether | C22H33BrO3Si | 详情 | 详情 | |
| (XXXIV) | 46087 | 3-[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-methyl-3-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-2-propyn-1-ol | C31H49BrO5Si | 详情 | 详情 | |
| (XXXV) | 46088 | 3-[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-methyl-3-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-2-propyn-1-one | C31H47BrO5Si | 详情 | 详情 | |
| (XXXVI) | 46089 | 1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-3-[(2S,3R,6R)-3-hydroxy-6-(hydroxymethyl)-2-methyltetrahydro-2H-pyran-2-yl]-1-propanone | C18H31BrO5 | 详情 | 详情 |
合成路线5
该中间体在本合成路线中的序号：(XXIV)Assembly of the target compound: The protection of the lactone (XXI) with benzyl trichloroacetimidate gives the benzyl ether (XXII), which is reduced with DIBAL in toluene to yield the lactol (XXIII). The reaction of (XXIII) with phosphorane (XXIV) in refluxing benzene affords the hydroxy-heptenoic ester (XXV), which is treated with Tbdms-Cl and imidazole to provide the silyl ether (XXVI). The reduction of the ester group of (XXVI) with DIBAL in dichloromethane furnishes the allylic alcohol (XXVII), which by a Sharpless asymmetric epoxidation gives the epoxyalcohol (XXVIII). The oxidation of the OH group of (XXVIII) with SO3/pyridine complex yields the epoxyaldehyde (XXIX), which by reaction with tetrabromomethane, PPh3 and TEA in dichloromethane affords the dibromovinyl derivative (XXX). The reaction of (XXX) with TBAF in THF provides the bromoacetylenic compound (XXXI), which is cyclized by means of BF3/Et2O complex in dichloromethane, furnishing the acetylenic tetrahydropyran (XXXII). The reaction of (XXXII) with Tes-Cl and imidazole in DMF gives the silyl ether (XXXIII), which is condensed with the intermediate carbaldehyde (IV) by means of CrCl2 in DMF to yield the propargyl alcohol (XXXIV). The oxidation of the OH group of (XXXIV) with MnO2 affords the corresponding ketone (XXXV), which is hydrogenated and deprotected with H2 over Pd/C in methanol to provide the saturated dihydroxyketone (XXXVI).
| 【1】 Forsyth, G.J.; Gonzalez, I.C.; Total synthesis of tryrsiferyl 23-acetate, a specific inhibitor of protein phosphatase 2A and anti-leukemic inducer of apoptosis. J Am Chem Soc 2000, 122, 38, 9099. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 40660 | CH5AlClN | 详情 | 详情 | ||
| (XXI) | 46090 | (5R)-5-(hydroxymethyl)dihydro-2(3H)-furanone | C5H8O3 | 详情 | 详情 | |
| (XXII) | 46076 | (5R)-5-[(benzyloxy)methyl]dihydro-2(3H)-furanone | C12H14O3 | 详情 | 详情 | |
| (XXIII) | 46077 | (5R)-5-[(benzyloxy)methyl]tetrahydro-2-furanol | C12H16O3 | 详情 | 详情 | |
| (XXIV) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XXV) | 46078 | ethyl (E,6R)-7-(benzyloxy)-6-hydroxy-2-methyl-2-heptenoate | C17H24O4 | 详情 | 详情 | |
| (XXVI) | 46079 | ethyl (E,6R)-7-(benzyloxy)-6-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-2-heptenoate | C23H38O4Si | 详情 | 详情 | |
| (XXVII) | 46080 | (E,6R)-7-(benzyloxy)-6-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-2-hepten-1-ol | C21H36O3Si | 详情 | 详情 | |
| (XXVIII) | 46081 | [(2R,3R)-3-((3R)-4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]butyl)-2-methyloxiranyl]methanol | C21H36O4Si | 详情 | 详情 | |
| (XXIX) | 46082 | (2S,3R)-3-((3R)-4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]butyl)-2-methyl-2-oxiranecarbaldehyde | C21H34O4Si | 详情 | 详情 | |
| (XXX) | 46083 | benzyl (2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-4-[(2R,3R)-3-(2,2-dibromovinyl)-3-methyloxiranyl]butyl ether; ([(1R)-1-[(benzyloxy)methyl]-3-[(2R,3R)-3-(2,2-dibromovinyl)-3-methyloxiranyl]propyl]oxy)(tert-butyl)dimethylsilane | C22H34Br2O3Si | 详情 | 详情 | |
| (XXXI) | 46084 | (2R)-1-(benzyloxy)-4-[(2R,3R)-3-(2-bromoethynyl)-3-methyloxiranyl]-2-butanol | C16H19BrO3 | 详情 | 详情 | |
| (XXXII) | 46085 | (2S,3R,6R)-6-[(benzyloxy)methyl]-2-(2-bromoethynyl)-2-methyltetrahydro-2H-pyran-3-ol | C16H19BrO3 | 详情 | 详情 | |
| (XXXIII) | 46086 | [[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-(2-bromoethynyl)-2-methyltetrahydro-2H-pyran-3-yl]oxy](triethyl)silane; benzyl [(2R,5R,6S)-6-(2-bromoethynyl)-6-methyl-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]methyl ether | C22H33BrO3Si | 详情 | 详情 | |
| (XXXIV) | 46087 | 3-[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-methyl-3-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-2-propyn-1-ol | C31H49BrO5Si | 详情 | 详情 | |
| (XXXV) | 46088 | 3-[(2S,3R,6R)-6-[(benzyloxy)methyl]-2-methyl-3-[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl]-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-2-propyn-1-one | C31H47BrO5Si | 详情 | 详情 | |
| (XXXVI) | 46089 | 1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-3-[(2S,3R,6R)-3-hydroxy-6-(hydroxymethyl)-2-methyltetrahydro-2H-pyran-2-yl]-1-propanone | C18H31BrO5 | 详情 | 详情 |
合成路线6
该中间体在本合成路线中的序号：(X)Synthesis of intermediate aldehyde (XV): The oxidation of 4-(benzyloxy)butanol (VIII) with oxalyl chloride gives the aldehyde (IX), which is condensed with 2-(triphenylphosphoranylidene)propionic acid ethyl ester (X) in hot THF to yield the unsaturated ester (XI). The enantioselective dihydroxylation of (XI) by means of AD-mix beta and methanesulfonamide in butanol/water affords the chiral dihydroxyester (XII), which is protected with 2,2-dimethoxypropane and CSA to provide the acetonide (XIII). The reduction of the ester group of (XIII) with DIBAL in THF gives the alcohol (XIV), which is finally oxidized with DMP to yield the desired intermediate aldehyde (XV).
| 【1】 Mulzer, J.; et al.; A novel highly stereoselective total synthesis of epothilone B and of its (12R,13R) acetonide. Tetrahedron Lett 2000, 41, 40, 7635. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VIII) | 46169 | 4-(benzyloxy)-1-butanol | C11H16O2 | 详情 | 详情 | |
| (IX) | 46170 | 4-(benzyloxy)butanal | C11H14O2 | 详情 | 详情 | |
| (X) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XI) | 46171 | ethyl (E)-6-(benzyloxy)-2-methyl-2-hexenoate | C16H22O3 | 详情 | 详情 | |
| (XII) | 46172 | ethyl (2S,3R)-6-(benzyloxy)-2,3-dihydroxy-2-methylhexanoate | C16H24O5 | 详情 | 详情 | |
| (XIII) | 46173 | ethyl (4S,5R)-5-[3-(benzyloxy)propyl]-2,2,4-trimethyl-1,3-dioxolane-4-carboxylate | C19H28O5 | 详情 | 详情 | |
| (XIV) | 46174 | [(4R,5R)-5-[3-(benzyloxy)propyl]-2,2,4-trimethyl-1,3-dioxolan-4-yl]methanol | C17H26O4 | 详情 | 详情 | |
| (XV) | 46175 | (4S,5R)-5-[3-(benzyloxy)propyl]-2,2,4-trimethyl-1,3-dioxolane-4-carbaldehyde | C17H24O4 | 详情 | 详情 |
合成路线7
该中间体在本合成路线中的序号：(II)In a different synthetic strategy, the known Garner's aldehyde (I) is subjected to a Wittig reaction with phosphorane (II) to give the unsaturated ester (III), which is subsequently hydrogenated, producing (IV) as an inseparable mixture of diastereoisomers. Oxazolidine hydrolysis in (IV), followed by cyclization under acidic conditions leads to lactone (V). This is then converted to the thiolactone (VI) upon treatment with Lawesson's reagent in hot toluene. Condensation of thiolactone (VI) with the Wittig reagent (VII), followed by double bond isomerization in the presence of DBU furnishes the dihydropyran derivative (VIII). Stereoselective hydrogenation of the double bond of (VIII) with PtO2 gives rise to the desired all-cis isomer (IX). The methyl vester group of (IX) is then reduced to aldehyde (X) by means of DIBAL in cold toluene.
| 【1】 Horigome, M.; Motoyoshi, H.; Watanabe, H.; Kitahara, T.; A synthesis of FR901464. Tetrahedron Lett 2001, 42, 46, 8207. |
| 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) | 62140 | tert-butyl (4S,5R)-4-formyl-2,2,5-trimethyl-1,3-oxazolidine-3-carboxylate | C12H21NO4 | 详情 | 详情 | |
| (II) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (III) | 62141 | tert-butyl (4R,5R)-4-[(E)-3-ethoxy-2-methyl-3-oxo-1-propenyl]-2,2,5-trimethyl-1,3-oxazolidine-3-carboxylate | C17H29NO5 | 详情 | 详情 | |
| (IV) | 62142 | tert-butyl (4R,5R)-4-(3-ethoxy-2-methyl-3-oxopropyl)-2,2,5-trimethyl-1,3-oxazolidine-3-carboxylate | C17H31NO5 | 详情 | 详情 | |
| (V) | 62143 | tert-butyl (2R,3R)-2,5-dimethyl-6-oxotetrahydro-2H-pyran-3-ylcarbamate | C12H21NO4 | 详情 | 详情 | |
| (VI) | 62144 | tert-butyl (2R,3R,5R)-2,5-dimethyl-6-thioxotetrahydro-2H-pyran-3-ylcarbamate | C12H21NO3S | 详情 | 详情 | |
| (VII) | 14689 | Methyl (triphenylphosphoranylidene)acetate; (methoxycarbonylmethylene)triphenylphosphorane；Methyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate | 2605-67-6 | C21H19O2P | 详情 | 详情 |
| (VIII) | 62145 | methyl 2-{(2R,3R)-3-[(tert-butoxycarbonyl)amino]-2,5-dimethyl-3,4-dihydro-2H-pyran-6-yl}acetate | C15H25NO5 | 详情 | 详情 | |
| (IX) | 62146 | methyl 2-{(2S,3S,5R,6R)-5-[(tert-butoxycarbonyl)amino]-3,6-dimethyltetrahydro-2H-pyran-2-yl}acetate | C15H27NO5 | 详情 | 详情 | |
| (X) | 62147 | tert-butyl (2R,3R,5S,6S)-2,5-dimethyl-6-(2-oxoethyl)tetrahydro-2H-pyran-3-ylcarbamate | C14H25NO4 | 详情 | 详情 |
合成路线8
该中间体在本合成路线中的序号：(II)Wittig reaction of aldehyde (X) with phosphorane (II) produces the unsaturated ester (XI), which is further reduced to the allylic alcohol (XII) with DIBAL in toluene. Treatment of (XII) with CBr4 and PPh3 leads to allyl bromide (XIII). This is then condensed with sodium p-toluenesulfinate (XIV), providing sulfone (XV). Subsequent acidic Boc group cleavage gives amine (XVI).
| 【1】 Horigome, M.; Motoyoshi, H.; Watanabe, H.; Kitahara, T.; A synthesis of FR901464. Tetrahedron Lett 2001, 42, 46, 8207. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (II) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (X) | 62147 | tert-butyl (2R,3R,5S,6S)-2,5-dimethyl-6-(2-oxoethyl)tetrahydro-2H-pyran-3-ylcarbamate | C14H25NO4 | 详情 | 详情 | |
| (XI) | 62148 | ethyl (E)-4-{(2S,3S,5R,6R)-5-[(tert-butoxycarbonyl)amino]-3,6-dimethyltetrahydro-2H-pyran-2-yl}-2-methyl-2-butenoate | C19H33NO5 | 详情 | 详情 | |
| (XII) | 62149 | tert-butyl (2R,3R,5S,6S)-6-[(E)-4-hydroxy-3-methyl-2-butenyl]-2,5-dimethyltetrahydro-2H-pyran-3-ylcarbamate | C17H31NO4 | 详情 | 详情 | |
| (XIII) | 62150 | tert-butyl (2R,3R,5S,6S)-6-[(E)-4-bromo-3-methyl-2-butenyl]-2,5-dimethyltetrahydro-2H-pyran-3-ylcarbamate | C17H30BrNO3 | 详情 | 详情 | |
| (XIV) | 62151 | 4-methylbenzenesulfinate | C7H7O2S | 详情 | 详情 | |
| (XV) | 62152 | tert-butyl (2R,3R,5S,6S)-2,5-dimethyl-6-{(E)-3-methyl-4-[(4-methylphenyl)sulfonyl]-2-butenyl}tetrahydro-2H-pyran-3-ylcarbamate | C24H37NO5S | 详情 | 详情 | |
| (XVI) | 62153 | (2R,3R,5S,6S)-2,5-dimethyl-6-{(E)-3-methyl-4-[(4-methylphenyl)sulfonyl]-2-butenyl}tetrahydro-2H-pyran-3-amine; (2R,3R,5S,6S)-2,5-dimethyl-6-{(E)-3-methyl-4-[(4-methylphenyl)sulfonyl]-2-butenyl}tetrahydro-2H-pyran-3-ylamine | C19H29NO3S | 详情 | 详情 |
合成路线9
该中间体在本合成路线中的序号：(VIII)A stereoselective synthesis of beta-elemene has been reported: Reaction of 2-allylpropane-1,3-diol (I) with tosyl chloride and pyridine gives the ditosylate (II), which is treated with NaCN in refluxing DMF to yield the dinitrile (III). The methanolysis of (III) with TsOH and refluxing methanol affords the dicarboxylic acid (IV), which is reduced with LiAlH4 in THF providing 3-allyl-1,5-pentanediol (V). The reaction of (V) with CBr4 and PPh3 in dichloromethane gives the dibromide (VI), which is ozonolyzed with ozone and PPh3 in dichloromethane to yield the aldehyde (VII). Condensation of (VII) with the phosphorane (VIII) in dichloromethane affords the unsaturated ester (IX), which is reduced with DIBAL in toluene to afford alcohol (X). Condensation of (X) with triethyl orthopropionate (XI) in refluxing phenol/toluene gives the anti-dibromoester (XII), along with some syn-isomer that is easily separated. Cyclization of (XII) with LDA in THF yields the cyclohexanecarboxylate (XIII), which is treated with t-BuOK in THF to afford the divinylcylohexanecarboxylate (XIV). Reduction of (XV) with DIBAL in toluene provides the carbinol (XV), which is treated with CuCl, PdCl2 and O2 in DMF/water giving the acetyl derivative (XVI). Oxidation of (XVI) with PCC and AcONa in dichloromethane gives keto-aldehyde (XVII), which is finally submitted to a double Wittig methylenation with methylenetriphenylphosphorane (XVIII) in THF.
| 【1】 Lee, J.; Kim, S.; Kim, D.; Chang, J.; Stereoselective synthesis of (±)-beta-elemene by a doubly diastereodifferentiating internal alkylation: A remarkable difference in the rate of enolization between syn and anti esters. Tetrahedron 2001, 57, 7, 1247. |
| 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) | 45745 | 2-allyl-1,3-propanediol | C6H12O2 | 详情 | 详情 | |
| (II) | 45746 | 2-([[(4-methylphenyl)sulfonyl]oxy]methyl)-4-pentenyl 4-methylbenzenesulfonate | C20H24O6S2 | 详情 | 详情 | |
| (III) | 45747 | 3-allylpentanedinitrile | C8H10N2 | 详情 | 详情 | |
| (IV) | 45748 | dimethyl 3-allylpentanedioate | C10H16O4 | 详情 | 详情 | |
| (V) | 45749 | 3-allyl-1,5-pentanediol | C8H16O2 | 详情 | 详情 | |
| (VI) | 45750 | 6-bromo-4-(2-bromoethyl)-1-hexene | C8H14Br2 | 详情 | 详情 | |
| (VII) | 45751 | 5-bromo-3-(2-bromoethyl)pentanal | C7H12Br2O | 详情 | 详情 | |
| (VIII) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (IX) | 45752 | ethyl (E)-7-bromo-5-(2-bromoethyl)-2-methyl-2-heptenoate | C12H20Br2O2 | 详情 | 详情 | |
| (X) | 45753 | (E)-7-bromo-5-(2-bromoethyl)-2-methyl-2-hepten-1-ol | C10H18Br2O | 详情 | 详情 | |
| (XI) | 10395 | 1,1,1-Triethoxypropane; 1,1-Diethoxypropyl ethyl ether; Triethyl orthopropionate | 115-80-0 | C9H20O3 | 详情 | 详情 |
| (XII) | 45754 | ethyl (2R,3R)-3-[4-bromo-2-(2-bromoethyl)butyl]-2,4-dimethyl-4-pentenoate | C15H26Br2O2 | 详情 | 详情 | |
| (XIII) | 45755 | ethyl (1R,2S,4R)-4-(2-bromoethyl)-2-isopropenyl-1-methylcyclohexanecarboxylate | 74181-34-3 | C15H25BrO2 | 详情 | 详情 |
| (XIV) | 45756 | ethyl (1R,2S,4R)-2-isopropenyl-1-methyl-4-vinylcyclohexanecarboxylate | C15H24O2 | 详情 | 详情 | |
| (XV) | 45757 | [(1R,2S,4R)-2-isopropenyl-1-methyl-4-vinylcyclohexyl]methanol | C13H22O | 详情 | 详情 | |
| (XVI) | 45758 | 1-[(1R,3S,4R)-4-(hydroxymethyl)-3-isopropenyl-4-methylcyclohexyl]-1-ethanone | C13H22O2 | 详情 | 详情 | |
| (XVII) | 45759 | (1R,2S,4R)-4-acetyl-2-isopropenyl-1-methylcyclohexanecarbaldehyde | C13H20O2 | 详情 | 详情 | |
| (XVIII) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 |
合成路线10
该中间体在本合成路线中的序号：(XVII)The glycosyl intermediates (VIIIb) and (VIIIc) can be prepared by several related methods. Wittig condensation of 2,3-O-isopropylidene-D-glyceraldehyde (XVI) with (1-carbethoxyethylidene)triphenylphosphorane (XVII) in dry CH2Cl2 provides the unsaturated ester (XVIII) (7). Diastereoselective dihydroxylation of (XVIII) to give diol (XIX) is accomplished using a variety of reagents, including Sharpless oxidation with AD-mix-beta/methanesulfonamide (7), NMMO or t-BuOOH and catalytic OsO4, K3Fe(CN)6 and catalytic K2OsO2(OH)4, tetradecyltrimethylammonium permanganate (TDTAP) and KMnO4, optionally in the presence of crown ether or RuCl3/CeCl3/NaIO4 (4) and NaMnO4/NaHCO3 (5). After conversion of dihydroxy ester (XIX) to the cyclic sulfite (XX) by means of SOCl2 and Et3N, oxidation employing TEMPO/NaOCl or RuCl3/NaIO4 provides the correspondng sulfate ester (XXI). Ring opening of the cyclic sulfate (XXI) with HF-triethylamine complex or with tetrabutyl- or tetraethylammonium fluoride produces the respective ammonium fluorosulfates (XXIIa-c), which undergo cyclization to fluorolactone (XXXIII) under acidic conditions. Subsequent acylation of the dihydroxy ribonolactone (XXIII) with benzoyl chloride and DMAP followed by reduction of the resulting dibenzoyloxy lactone (XXIV) with either Red-Al or LiAlH(O-t-Bu)3 yields lactol (XXV) (4, 5), which is either acetylated to (VIIIb) using Ac2O and DMAP in THF (4) or chlorinated to (VIIIc) with sulfuryl chloride and TBAB (5). Alternatively, cyclization and deprotection of dihydroxy ester (XIX) with ethanolic HCl leads to 2-methyl-D-arabino-γ-lactone (XXVI), which, after protection as the dibenzoate ester (XXVII) with benzoyl chloride in dry pyridine, is fluorinated to (XXIV) using either diethylaminosulfur trifluoride (DAST) or bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor) in THF (7). In a further method, dihydroxy ester (XIX) is selectively acylated at the secondary hydroxyl group with benzoyl chloride in pyridine to produce compound (XXVIII), which is fluorinated to (XXIX) by treatment with DAST or Deoxofluor in THF. Deprotection and cyclization of compound (XXIX) with TFA in hot CH3CN/H2O gives 3-O-benzoyl-2-methyl-2-deoxy-2-fluoro-D-ribono-γ-lactone (XXX), which is further benzoylated to (XXIV) by means of benzoyl chloride n the presence of DMAP and pyridine in AcOEt (7). Scheme 3.
| 【4】 Chun, B.-K., Wang, P. (Pharmasset, Inc.). Preparation of 2’-fluoro-2’-alkyl-substituted or other optionally substituted ribofuranosyl pyrimidines and purines and their derivatives. WO 2006031725. |
| 【5】 Axt, S.D., Sarma, K., Vitale, J. et al. (Pharmasset, Inc.; F. Hoffmann La Roche AG). Preparation of nucleosides ribofuranosyl pyrimidines. WO 2008045419. |
| 【7】 Wang, P., Stec, W., Clark, J., Chun, B.-K., Shi, J., Du, J. (Pharmasset, Inc.). Preparation of alkyl-substituted 2-deoxy-2-fluoro-D-ribofuranosyl pyrimidines and purines and their derivatives. WO 2006012440. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXIIA) | 65923 | triethylammonium (1R,2S)-1-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-ethoxy-2-fluoro-2-methyl-3-oxopropyl sulfate | C17H34FNO8S | 详情 | 详情 | |
| (XXIIB) | 65924 | C27H54FNO8S | 详情 | 详情 | ||
| (XXIIC) | 65925 | C19H38FNO8S | 详情 | 详情 | ||
| (VIIIB) | 65912 | C22H21FO6 | 详情 | 详情 | ||
| (VIIIC) | 65913 | C20H17ClFO5 | 详情 | 详情 | ||
| (XVI) | 36759 | (4R)-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde | 15186-48-8 | C6H10O3 | 详情 | 详情 |
| (XVII) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XVIII) | 65919 | (2E)-3-[(4R)-2,2-Dimethyl-1,3-dioxolan-4-yl]-2-methyl-2-propenoic acid ethyl ester | C11H18O4 | 详情 | 详情 | |
| (XIX) | 65920 | (2S,3R)-3-((4R)-2,2-Dimethyldioxolan-4-yl)-2-methyl-2,3-dihydroxypropanoic acid ethyl ester | 93635-76-8 | C11H20O6 | 详情 | 详情 |
| (XX) | 65921 | (4S,5S)-ethyl 5-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-4-methyl-1,3,2-dioxathiolane-4-carboxylate 2-oxide | C11H18O7S | 详情 | 详情 | |
| (XXI) | 65922 | (4S,5S)-ethyl 5-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-4-methyl-1,3,2-dioxathiolane-4-carboxylate 2,2-dioxide | C11H18O8S | 详情 | 详情 | |
| (XXIII) | 65926 | (3R,4R,5R)-3-Fluoro-4-hydroxy-5-(hydroxymethyl)-3-methyloxolan-2-one; (2R)-2-Deoxy-2-fluoro-2-methyl-D-erythro-pentonic acid gamma-lactone | 879551-04-9 | C6H9FO4 | 详情 | 详情 |
| (XXIV) | 65927 | (2R)-2-Deoxy-2-fluoro-2-methyl-D-erythropentonic acid gamma-lactone 3,5-dibenzoate | 874638-80-9 | C20H17FO6 | 详情 | 详情 |
| (XXV) | 65928 | C20H19FO6 | 详情 | 详情 | ||
| (XXVI) | 65929 | 2-C-Methyl-D-ribono-1,4-lactone; 3,4-Dihydroxy-5-(hydroxymethyl)-3-methyloxolan-2-one | 492-30-8 | C6H10O5 | 详情 | 详情 |
| (XXVII) | 65930 | C20H18O7 | 详情 | 详情 | ||
| (XXVIII) | 65931 | C18H24O7 | 详情 | 详情 | ||
| (XXIX) | 65932 | C18H23FO6 | 详情 | 详情 | ||
| (XXX) | 65933 | C13H13FO5 | 详情 | 详情 |