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【结 构 式】 
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【分子编号】26485 【品名】1-(dimethoxymethyl)-4-methoxybenzene 【CA登记号】2186-92-7 |
【 分 子 式 】C10H14O3 【 分 子 量 】182.21936 【元素组成】C 65.92% H 7.74% O 26.34% |
合成路线1
该中间体在本合成路线中的序号：(VII)Synthesis of the intermediate butyraldehyde (X): The Sharpless asymmetric epoxidation of 2(E)-buten-1-ol by means of t-Bu-OOH and D-(-9-diisopropyl tartrate gives the epoxy alcohol (II), which is treated with Tbdps-Cl, TEA and DMAP to yield the silyl ether (III) The condensation of (III) with 1,3-dithiane (IV) by means of BuLi in THF/HMPA affords the cyclic thioketal (V), which is deprotected by means of TBAF in THF, affording the diol (VI). The reaction of (VI) with 4-methoxybenzaldehyde dimethylacetal (VII) by means of TsOH in DMF provides the benzylidene ketal (VIII), which is submitted to a selective opening by means of DIBAL in dichloromethane to give the secondary benzyl ether (IX). Finally this compound is oxidized with SO3/Pyridine and TEA in DMSO/dichloromethane to obtain the target intermediate, the chiral butyraldehyde (X).
| 【1】 Chen, K.; Formal total synthesis of (-)-FK506. Diss Abstr Int B - Sci Eng 1993, 53, 9, 4663. |
| 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) | 54882 | 2-Butene-1-ol; Crotyl Alcohol; trans-Propenylcarbinol | 504-61-0 | C4H8O | 详情 | 详情 |
| (II) | 57330 | [(2R,3R)-3-methyloxiranyl]methanol | C4H8O2 | 详情 | 详情 | |
| (III) | 14956 | tert-butyl[[(2R,3R)-3-methyloxiranyl]methoxy]diphenylsilane; tert-butyl(diphenyl)silyl [(2R,3R)-3-methyloxiranyl]methyl ether | C20H26O2Si | 详情 | 详情 | |
| (IV) | 42372 | 1,3-dithiane | 505-23-7 | C4H8S2 | 详情 | 详情 |
| (V) | 57331 | (2S,3S)-1-{[tert-butyl(diphenyl)silyl]oxy}-3-(1,3-dithian-2-yl)-2-butanol | C24H34O2S2Si | 详情 | 详情 | |
| (VI) | 57332 | (2S,3S)-3-(1,3-dithian-2-yl)-1,2-butanediol | C8H16O2S2 | 详情 | 详情 | |
| (VII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (VIII) | 57333 | (4S)-4-[(1S)-1-(1,3-dithian-2-yl)ethyl]-2-(4-methoxyphenyl)-1,3-dioxolane; 4-{(4S)-4-[(1S)-1-(1,3-dithian-2-yl)ethyl]-1,3-dioxolan-2-yl}phenyl methyl ether | C16H22O3S2 | 详情 | 详情 | |
| (IX) | 57334 | (2S,3S)-3-(1,3-dithian-2-yl)-2-[(4-methoxybenzyl)oxy]-1-butanol | C16H24O3S2 | 详情 | 详情 | |
| (X) | 57335 | (2S,3S)-3-(1,3-dithian-2-yl)-2-[(4-methoxybenzyl)oxy]butanal | C16H22O3S2 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XXVI)The intermediate (XLI) has been obtained as follows: The condensation of the silylated propionic aldehyde (I) with the chiral allene (XXIII) by means of BF3/Et2O gives the acetylenic alcohol (XXIV), which is desilylated with TBAF, yielding the diol (XXV). The reaction of (XXV) with p-methoxybenzaldehyde dimethyl acetal (XXVI) affords the cyclic ketal (XXVII), which is treated with Red-Al to provided the primary alcohol (XXVIII). The asymmetric Sharpless epoxidation of the double bond of (XXVIII) gives the epoxide (XXIX), which is methylated with Me2CuCNLi2, yielding the chiral diol (XXX). The regioselective acylation of (XXX) with pivaloyl chloride affords the monopivalate (XXXI), which is silylated with Tes-Otf, providing the silyl ether (XXXII). The reductive cleavage of the pivalate ester of (XXXII) with Red-Al furnishes the primary alcohol (XXXIII), which is oxidized with DMP to the aldehyde (XXXIV). The condensation of (XXXIV) with the bromoallyl compound (XXXV) gives the homoallyl alcohol (XXXVI), which is treated with NaH in THF to afford the conjugated diene (XXXVII) (2). The reductive cleavage of the cyclic ketal group of (XXXVII) with iBu2AlH gives the primary alcohol (XXXVIII), which is treated with I2 and PPh3 to yield the iodo derivative (XXXIX). Finally, this compound is condensed with 9-methoxy-9-borabicyclo[3,3,1]nonane (XL) by means of BuLi in THF/ethyl ether to furnish the desired intermediate, the lithium salt (XLI).
| 【1】 Marshall, J.A.; Hohns, B.A.; Total synthesis of (+)-discodermolide. J Org Chem 1998, 63, 22, 7885. |
| 【2】 Marsshall, J.A.; et al.; Synthesis of discodermolide subunits by SE2' addition of nonracemic allenylstannanes to aldehydes. J Org Chem 1998, 63, 3, 817. |
| 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) | 42735 | (2S)-2-methyl-3-[(triethylsilyl)oxy]propanal | C10H22O2Si | 详情 | 详情 | |
| (XXIII) | 42756 | 2-(tributylstannyl)-2,3-pentadienyl pivalate | C22H42O2Sn | 详情 | 详情 | |
| (XXIV) | 42757 | (4R,5S,6S)-5-hydroxy-4,6-dimethyl-7-[(triethylsilyl)oxy]-2-heptynyl pivalate | C20H38O4Si | 详情 | 详情 | |
| (XXV) | 42758 | (4R,5S,6S)-5,7-dihydroxy-4,6-dimethyl-2-heptynyl pivalate | C14H24O4 | 详情 | 详情 | |
| (XXVI) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XXVII) | 42759 | (4R)-4-[(2R,4S,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-pentynyl pivalate | C22H30O5 | 详情 | 详情 | |
| (XXVIII) | 42760 | (E,4R)-4-[(2R,4S,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-penten-1-ol | C17H24O4 | 详情 | 详情 | |
| (XXIX) | 42761 | ((2S,3R)-3-[(1R)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]oxiranyl)methanol | C17H24O5 | 详情 | 详情 | |
| (XXX) | 42762 | (2S,3S,4R)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-1,3-pentanediol | C18H28O5 | 详情 | 详情 | |
| (XXXI) | 42763 | (2S,3S,4R)-3-hydroxy-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methylpentyl pivalate | C23H36O6 | 详情 | 详情 | |
| (XXXII) | 42764 | (2S,3S,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]pentyl pivalate | C29H50O6Si | 详情 | 详情 | |
| (XXXIII) | 42765 | (2S,3S,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]-1-pentanol | C24H42O5Si | 详情 | 详情 | |
| (XXXIV) | 42766 | (2R,3R,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]pentanal | C24H40O5Si | 详情 | 详情 | |
| (XXXV) | 42629 | (1-bromo-2-propenyl)(trimethyl)silane | 94397-40-7 | C6H13BrSi | 详情 | 详情 |
| (XXXVI) | 42767 | (3S,4R,5S,6S,7S)-7-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-5-methyl-6-[(triethylsilyl)oxy]-3-(trimethylsilyl)-1-octen-4-ol | C30H54O5Si2 | 详情 | 详情 | |
| (XXXVII) | 42768 | triethyl[((1S,2S,3Z)-1-[(1S)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]-2-methyl-3,5-hexadienyl)oxy]silane; 4-((2R,4R,5S)-4-[(1S,2S,3S,4Z)-1,3-dimethyl-2-[(triethylsilyl)oxy]-4,6-heptadienyl]-5-methyl-1,3-dioxan-2-yl)phenyl methyl ether | C27H44O4Si | 详情 | 详情 | |
| (XXXVIII) | 42769 | (2S,3R,4S,5S,6S,7Z)-3-[(4-methoxybenzyl)oxy]-2,4,6-trimethyl-5-[(triethylsilyl)oxy]-7,9-decadien-1-ol | C27H46O4Si | 详情 | 详情 | |
| (XXXIX) | 42770 | triethyl[((1S,2S,3Z)-1-[(1S,2S,3R)-4-iodo-2-[(4-methoxybenzyl)oxy]-1,3-dimethylbutyl]-2-methyl-3,5-hexadienyl)oxy]silane; (1S,2S,3Z)-1-[(1S,2S,3R)-4-iodo-2-[(4-methoxybenzyl)oxy]-1,3-dimethylbutyl]-2-methyl-3,5-hexadienyl triethylsilyl ether | C27H45IO3Si | 详情 | 详情 | |
| (XL) | 42771 | 9-methoxy-9-borabicyclo[3.3.1]nonane | 38050-71-4 | C9H17BO | 详情 | 详情 |
| (XLI) | 42772 | C36H62BLiO4Si | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(XVIII)The oxidation of the lactol (XIII) with Br2 and BaCO3 gives the lactone (XIV), which is stereoselectively alkylated with allyl bromide (XV) by means of LDA in HMPA to yield lactone (XVI). The opening of the lactone ring of (XVI) with MeONa affords the dihydroxyester (XVII), which is protected by reaction with anisaldehyde dimethylacetal (XVIII) and CSA to provide the benzylidene derivative (XIX). The reduction of the ester group of (XIX) with LiAlH4 gives the corresponding carbinol (XX), which is acylated with Ms-Cl and TEA to yield the mesylate (XXI). The reduction of the mesyloxy group of (XXI) with LiAlH4 affords the dimethyl compound (XXII), which is submitted to a regioselective cleavage of the Pmp protecting group by means of DIBAL in toluene to provide the primary alcohol (XXIII). The oxidation of (XXIII) with DMP gives the corresponding aldehyde (XXIV), which is condensed with tert-butyl isobutyrylacetate (XXV) by means of NaH and BuLi to yield the unsaturated ketoester (XXVI). Stereoselective reduction of the beta-oxo group of (XXVI) by means of Me4NBH(OAc)3 affords the desired diol (XXVII), which is regioselectively silylated at the beta-hydroxy group by means of Tbdms-OTf to provide the monosilyl ether (XXVIII). The oxidation of the remaining hydroxy group of (XXVIII) by means of DMP gives the unsaturated ketoester (XXIX).
| 【1】 Wong, C.-H.; Liu, J.; Aldolase-catalyzed asymmetric synthesis of novel pyranose synthons as a new entry to heterocycles and epothilones. Angew Chem. Int Ed 2002, 41, 8, 1404. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIII) | 54267 | (4S,5S)-5-methyltetrahydro-2H-pyran-2,4-diol | C6H12O3 | 详情 | 详情 | |
| (XIV) | 54268 | (4S,5S)-4-hydroxy-5-methyltetrahydro-2H-pyran-2-one | C6H10O3 | 详情 | 详情 | |
| (XV) | 11463 | 3-Bromo-1-propene; 3-Bromopropene；allyl bromide | 106-95-6 | C3H5Br | 详情 | 详情 |
| (XVI) | 54269 | (3S,4R,5S)-3-allyl-4-hydroxy-5-methyltetrahydro-2H-pyran-2-one | C9H14O3 | 详情 | 详情 | |
| (XVII) | 54270 | methyl (2S)-2-[(1R,2S)-1,3-dihydroxy-2-methylpropyl]-4-pentenoate | C10H18O4 | 详情 | 详情 | |
| (XVIII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XIX) | 54271 | methyl (2S)-2-[(4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-4-pentenoate | n/a | C18H24O5 | 详情 | 详情 |
| (XX) | 54272 | (2R)-2-[(4S,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-4-penten-1-ol | n/a | C17H24O4 | 详情 | 详情 |
| (XXI) | 54273 | (2R)-2-[(4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-4-pentenyl methanesulfonate | n/a | C18H26O6S | 详情 | 详情 |
| (XXII) | 54274 | (4S,5S)-2-(4-methoxyphenyl)-5-methyl-4-[(1S)-1-methyl-3-butenyl]-1,3-dioxane; methyl 4-{(4S,5S)-5-methyl-4-[(1S)-1-methyl-3-butenyl]-1,3-dioxan-2-yl}phenyl ether | n/a | C17H24O3 | 详情 | 详情 |
| (XXIII) | 54275 | (2S,3S,4S)-3-[(4-methoxybenzyl)oxy]-2,4-dimethyl-6-hepten-1-ol | n/a | C17H26O3 | 详情 | 详情 |
| (XXIV) | 54276 | (2R,3S,4S)-3-[(4-methoxybenzyl)oxy]-2,4-dimethyl-6-heptenal | n/a | C17H24O3 | 详情 | 详情 |
| (XXV) | 54277 | tert-butyl 4-methyl-3-oxopentanoate | 94250-54-1 | C10H18O3 | 详情 | 详情 |
| (XXVI) | 54278 | tert-butyl (5S,6S,7S,8S)-5-hydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-3-oxo-10-undecenoate | n/a | C27H42O6 | 详情 | 详情 |
| (XXVII) | 54279 | tert-butyl (3S,5S,6S,7S,8S)-3,5-dihydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-10-undecenoate | n/a | C27H44O6 | 详情 | 详情 |
| (XXVIII) | 54280 | tert-butyl (3S,5S,6S,7S,8S)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-hydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-10-undecenoate | n/a | C33H58O6Si | 详情 | 详情 |
| (XXIX) | 54281 | tert-butyl (3S,6R,7S,8S)-3-{[tert-butyl(dimethyl)silyl]oxy}-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-5-oxo-10-undecenoate | n/a | C33H56O6Si | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(XIV)The condensation of decanal (I) with silyl enol ether (II) by means of a chiral catalyst and Sn(OTf)2 in dichloromethane gives the chiral thiocarboxylic ester (III), which is treated with chlorothioformate (IV) and pyridine in refluxing dichloroethane to yield the thiocarbonic ester (V). The reduction of (V) with Bu3SnH and AIBN in refluxing toluene affords the chiral thioester (VI), which is reduced with LiAlH4 in THF to provide the alcohol (VII). The oxidation of (VII) with oxalyl chloride in DMSO/dichloromethane gives the corresponding aldehyde (VIII), which is condensed with phosphorane (IX) to yield the unsaturated ester (X). The reduction of the ester group of (X) with DIBAL in dichloromethane affords the allyl alcohol (XI), which is submitted to a Sharpless epoxidation with tert-butyl hydroperoxide (TBHP) and Ti(O-iPr)4 in the presence of diethyl D-tartrate, providing the chiral epoxide (XII). Methylation of the epoxide ring of (XII) with MeLi and CuI in ethyl ether gives the diol (XIII), which is treated with the dimethyl acetal (XIV) and Ts-OH in dichloromethane to yield the 1,3-dioxane (XV). The reductive cleavage of (XV) with DIBAL in the same solvent affords the Pmb ether (XVI), whose primary alcohol is oxidized with oxalyl chloride in DMSO/dichloromethane to provide the aldehyde (XVII). The condensation of (XVII) with phosphorane (XVIII) in refluxing THF gives the unsaturated ester (XIX).
| 【1】 Wakabayashi, T.; Mori, K.; Kobayashi, S.; Total synthesis and structural elucidation of khafrefungin. J Am Chem Soc 2001, 123, 7, 1372. |
| 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) | 31059 | decanal | 112-31-2 | C10H20O | 详情 | 详情 |
| (II) | 47158 | (Z)-1-(propylsulfanyl)-1-propenyl trimethylsilyl ether; trimethyl[[(Z)-1-(propylsulfanyl)-1-propenyl]oxy]silane | C9H20OSSi | 详情 | 详情 | |
| (III) | 47159 | S-propyl (2S,3R)-3-hydroxy-2-methyldodecanethioate | C16H32O2S | 详情 | 详情 | |
| (IV) | 25805 | 1-[(chlorocarbothioyl)oxy]benzene; Phenylchlorothioformate | 1005-56-7 | C7H5ClOS | 详情 | 详情 |
| (V) | 47160 | S-propyl (2S,3R)-2-methyl-3-[(phenoxycarbothioyl)oxy]dodecanethioate | C23H36O3S2 | 详情 | 详情 | |
| (VI) | 47161 | S-propyl (2S)-2-methyldodecanethioate | C16H32OS | 详情 | 详情 | |
| (VII) | 47162 | (2S)-2-methyl-1-dodecanol | C13H28O | 详情 | 详情 | |
| (VIII) | 47163 | (2S)-2-methyldodecanal | C13H26O | 详情 | 详情 | |
| (IX) | 47164 | propyl 2-(triphenylphosphoranylidene)acetate | C23H23O2P | 详情 | 详情 | |
| (X) | 47165 | propyl (E,4S)-4-methyl-2-tetradecenoate | C18H34O2 | 详情 | 详情 | |
| (XI) | 47166 | (E,4S)-4-methyl-2-tetradecen-1-ol | C15H30O | 详情 | 详情 | |
| (XII) | 47167 | [(2S,3R)-3-[(1S)-1-methylundecyl]oxiranyl]methanol | C15H30O2 | 详情 | 详情 | |
| (XIII) | 47168 | (2S,3R,4S)-2,4-dimethyl-1,3-tetradecanediol | C16H34O2 | 详情 | 详情 | |
| (XIV) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XV) | 47169 | (4R,5S)-2-(4-methoxyphenyl)-5-methyl-4-[(1S)-1-methylundecyl]-1,3-dioxane; methyl 4-[(4R,5S)-5-methyl-4-[(1S)-1-methylundecyl]-1,3-dioxan-2-yl]phenyl ether | C24H40O3 | 详情 | 详情 | |
| (XVI) | 47170 | (2S,3R,4S)-3-[(4-methoxybenzyl)oxy]-2,4-dimethyl-1-tetradecanol | C24H42O3 | 详情 | 详情 | |
| (XVII) | 47171 | (2R,3R,4S)-3-[(4-methoxybenzyl)oxy]-2,4-dimethyltetradecanal | C24H40O3 | 详情 | 详情 | |
| (XVIII) | 47172 | propyl 2-(triphenylphosphoranylidene)propanoate | C24H25O2P | 详情 | 详情 | |
| (XIX) | 47173 | propyl (E,4S,5R,6S)-5-[(4-methoxybenzyl)oxy]-2,4,6-trimethyl-2-hexadecenoate | C30H50O4 | 详情 | 详情 |
合成路线5
该中间体在本合成路线中的序号：(XXIII)2-Deoxy-D-glucose (XXII) is protected as the cyclic acetal (XXIV) employing p methoxybenzaldehyde dimethyl acetal (XXIII) in the presence of TsOH. Subsequent oxidation of the anomeric hydroxyl group of (XXIV) with Br2 leads to lactone (XXV). After protection of the remaining 3-hydroxyl group of (XXV) as the silyl ether (XXVI), olefination with the Tebbe reagent provides the exocyclic vinyl ether (XXVII). Treatment of (XXVII) with PPTS and MeOH affords a separable mixture of epimeric methylketals (XXVIII). Desilylation of the desired isomer yields alcohol (XXIX), which is then oxidized to ketone (XXX) employing the Dess-Martin periodinane reagent.
| 【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 |
|---|---|---|---|---|---|---|
| (XXII) | 62159 | (4R,5S,6R)-6-(hydroxymethyl)tetrahydro-2H-pyran-2,4,5-triol | C6H12O5 | 详情 | 详情 | |
| (XXIII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XXIV) | 62160 | (4aR,8R,8aS)-2-(4-methoxyphenyl)hexahydropyrano[3,2-d][1,3]dioxine-6,8-diol | C14H18O6 | 详情 | 详情 | |
| (XXV) | 62161 | (4aR,8R,8aS)-8-hydroxy-2-(4-methoxyphenyl)tetrahydropyrano[3,2-d][1,3]dioxin-6(4H)-one | C14H16O6 | 详情 | 详情 | |
| (XXVI) | 62162 | (4aR,8R,8aR)-8-{[tert-butyl(dimethyl)silyl]oxy}-2-(4-methoxyphenyl)tetrahydropyrano[3,2-d][1,3]dioxin-6(4H)-one | C20H30O6Si | 详情 | 详情 | |
| (XXVII) | 62163 | {[(4aR,8R,8aR)-2-(4-methoxyphenyl)-6-methylenehexahydropyrano[3,2-d][1,3]dioxin-8-yl]oxy}(tert-butyl)dimethylsilane; 4-((4aR,8R,8aR)-8-{[tert-butyl(dimethyl)silyl]oxy}-6-methylenehexahydropyrano[3,2-d][1,3]dioxin-2-yl)phenyl methyl ether | C21H32O5Si | 详情 | 详情 | |
| (XXVIII) | 62164 | 4-((4aR,8R,8aR)-8-{[tert-butyl(dimethyl)silyl]oxy}-6-methoxy-6-methylhexahydropyrano[3,2-d][1,3]dioxin-2-yl)phenyl methyl ether; {[(4aR,8R,8aR)-6-methoxy-2-(4-methoxyphenyl)-6-methylhexahydropyrano[3,2-d][1,3]dioxin-8-yl]oxy}(tert-butyl)dimethylsilane | C22H36O6Si | 详情 | 详情 | |
| (XXIX) | 62165 | (4aR,6S,8R,8aS)-6-methoxy-2-(4-methoxyphenyl)-6-methylhexahydropyrano[3,2-d][1,3]dioxin-8-ol | C16H22O6 | 详情 | 详情 | |
| (XXX) | 62166 | (4aR,6S,8aR)-6-methoxy-2-(4-methoxyphenyl)-6-methyltetrahydropyrano[3,2-d][1,3]dioxin-8(4H)-one | C16H20O6 | 详情 | 详情 |
合成路线6
该中间体在本合成路线中的序号：(XXVII)In a further procedure, hydroxy amino ester (VIII) was treated with anisaldehyde dimethyl acetal (XXVII) to provide oxazolidine (XXVIII) as a diastereomeric mixture. Ester hydrolysis of (XXVIII) with LiOH gave acid (XXIX), which was then coupled with taxane (XXX) to furnish ester (XXXI). Acidic treatment of (XXXI) cleaved the oxazolidine and deprotected the silyl ether group to produce (XXXII). Subsequent coupling of (XXXII) with acid (XXVII), followed by reductive deprotection of the trichloroethylcarbonyl group, provided intermediate (XXVI), which was finally converted into the title compound by hydrogenolysis in the presence of p-TsOH as above.
| 【1】 Tsujihari, K.; Hashiyama, T.; Ohashi, M.; Nakanishi, N. (Tanabe Seiyaku Co., Ltd.); Baccatin derivs. and processes for preparing the same. CA 2162759; EP 0712854; JP 1997151181; US 5589502 . |
| 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) | 26469 | methyl (2R,3S)-3-[(tert-butoxycarbonyl)amino]-3-cyclopropyl-2-hydroxypropanoate | C12H21NO5 | 详情 | 详情 | |
| (XXVI) | 26484 | (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4-(acetoxy)-2-(benzoyloxy)-1,9,12-trihydroxy-10,14,17,17-tetramethyl-11-oxo-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-15-yl (5S,12R)-5-(aminocarbonyl)-12-[(S)-[(tert-butoxycarbonyl)amino](cyclopropyl)methyl]-3,7,10-trioxo-1-phenyl-2,8,11-trioxa-4-azatridecan-13-oate | C54H67N3O20 | 详情 | 详情 | |
| (XXVII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XXVIII) | 26486 | 3-(tert-butyl) 5-methyl (4S,5R)-4-cyclopropyl-2-(4-methoxyphenyl)-1,3-oxazolidine-3,5-dicarboxylate | C20H27NO6 | 详情 | 详情 | |
| (XXIX) | 26487 | (4S,5R)-3-(tert-butoxycarbonyl)-4-cyclopropyl-2-(4-methoxyphenyl)-1,3-oxazolidine-5-carboxylic acid | C19H25NO6 | 详情 | 详情 | |
| (XXX) | 26488 | (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4-(acetoxy)-1,15-dihydroxy-10,14,17,17-tetramethyl-11-oxo-12-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-9-[(triethylsilyl)oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-2-yl benzoate | C38H51Cl3O12Si | 详情 | 详情 | |
| (XXXI) | 26489 | 5-[(1S,2S,3R,4S,7R,9S,10S,12R,15S)-4-(acetoxy)-2-(benzoyloxy)-1-hydroxy-10,14,17,17-tetramethyl-11-oxo-12-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-9-[(triethylsilyl)oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-15-yl] 3-(tert-butyl) (4S,5R)-4-cyclopropyl-2-(4-methoxyphenyl)-1,3-oxazolidine-3,5-dicarboxylate | C57H74Cl3NO17Si | 详情 | 详情 | |
| (XXXII) | 26490 | (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4-(acetoxy)-15-([(2R,3S)-3-[(tert-butoxycarbonyl)amino]-3-cyclopropyl-2-hydroxypropanoyl]oxy)-1,9-dihydroxy-10,14,17,17-tetramethyl-11-oxo-12-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-2-yl benzoate | C43H54Cl3NO16 | 详情 | 详情 | |
| (XXXIII) | 26491 | 2-[((3S)-4-amino-3-[[(benzyloxy)carbonyl]amino]-4-oxobutanoyl)oxy]acetic acid | C14H16N2O7 | 详情 | 详情 |
合成路线7
该中间体在本合成路线中的序号：(XXVII)In an alternative procedure, acid (XXVII) was activated as the mixed anhydride (XXXV) with isopropyl chloroformate (XXXIV), and then condensed with taxane intermediate (XIV) to give ester (XXVI). Hydrogenolytic deprotection of the N-carbobenzoy group of (XXVI) yielded the title compound.
| 【1】 Tsujihari, K.; Hashiyama, T.; Ohashi, M.; Nakanishi, N. (Tanabe Seiyaku Co., Ltd.); Baccatin derivs. and processes for preparing the same. CA 2162759; EP 0712854; JP 1997151181; US 5589502 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIV) | 26474 | methyl (9S,12S)-4-methoxy-12-[[(2S,5S,8S,11R)-5-(4-methoxybenzyl)-2,6,8,11,15,15-hexamethyl-4,7,10,13-tetraoxo-14-oxa-3,6,9,12-tetraazahexadec-1-anoyl](methyl)amino]-11-oxo-2-oxa-10-azatricyclo[12.2.2.1(3,7)]nonadeca-1(16),3(19),4,6,14,17-hexaene-9-carboxylate | C40H53NO14 | 详情 | 详情 | |
| (XXVI) | 26484 | (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4-(acetoxy)-2-(benzoyloxy)-1,9,12-trihydroxy-10,14,17,17-tetramethyl-11-oxo-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-15-yl (5S,12R)-5-(aminocarbonyl)-12-[(S)-[(tert-butoxycarbonyl)amino](cyclopropyl)methyl]-3,7,10-trioxo-1-phenyl-2,8,11-trioxa-4-azatridecan-13-oate | C54H67N3O20 | 详情 | 详情 | |
| (XXVII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XXXIV) | 26492 | 2-[(chlorocarbonyl)oxy]propane | 108-23-6 | C4H7ClO2 | 详情 | 详情 |
| (XXXV) | 26493 | 4-Amino-3(S)-(benzyloxycarbonylamino)-4-oxobutyric acid 2-(isopropoxycarbonyloxy)-2-oxoethyl ester | C18H22N2O9 | 详情 | 详情 |
合成路线8
该中间体在本合成路线中的序号：(VII)The known photoaddition-fragmentation product (I) was brominated with N-bromosuccinimide in the presence of AIBN to afford bromoester (II), which upon treatment with LiCl in refluxing DMF produced the unsaturated ester (III) with concomitant removal of the methyl carbonate. Subsequent mesylation of the hydroxyl group of (III), followed by elimination with DBU in boiling benzene led to the formation of the diene ester (IV). Selective epoxidation of (IV) with m-chloroperbenzoic acid yielded the epoxy-unsaturated ester (V), which was oxidized with OsO4 and N-methylmorpholine-N-oxide to the epoxy diol (VI). Reaction of (VI) with camphorsulfonic acid in wet CH2Cl2 gave the corresponding tetraol, which on exposure to p-anisaldehyde dimethyl acetal (VII) produced selectively the acetal (VIII). The reduction of the ester group of (VIII) with LiAlH4, followed by silylation with TBDPSi-Cl afforded the monosilylated compound (IX). The reaction of (IX) with SOCl2 in the presence of pyridine generated the cyclic sulfite ester (X), which was oxidized to sulfate (XI) using RuCl3 and NaIO4.
| 【1】 Winkler, J.D.; Lewin, N.E.; Blumberg, P.M.; Harrison, S.; Kim, S.; Synthesis and biological evaluation of highly functionalized analogues of ingenol. J Am Chem Soc 1999, 121, 2, 296. |
| 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) | 30276 | methyl (1S,4S,5S,9R)-4-[(methoxycarbonyl)oxy]-14-oxotricyclo[7.4.1.0(1,5)]tetradecane-7-carboxylate | C18H26O6 | 详情 | 详情 | |
| (II) | 30277 | methyl (1S,4S,5S,9R)-6-bromo-4-[(methoxycarbonyl)oxy]-14-oxotricyclo[7.4.1.0(1,5)]tetradecane-7-carboxylate | C18H25BrO6 | 详情 | 详情 | |
| (III) | 30278 | methyl (1S,4S,5S,9R)-4-hydroxy-14-oxotricyclo[7.4.1.0(1,5)]tetradec-6-ene-7-carboxylate | C16H22O4 | 详情 | 详情 | |
| (IV) | 30279 | methyl (1S,9R)-14-oxotricyclo[7.4.1.0(1,5)]tetradeca-4,6-diene-7-carboxylate | C16H20O3 | 详情 | 详情 | |
| (V) | 30280 | methyl (1S,4S,6R,10R)-15-oxo-5-oxatetracyclo[8.4.1.0(1,6).0(4,6)]pentadec-7-ene-8-carboxylate | C16H20O4 | 详情 | 详情 | |
| (VI) | 30281 | methyl (1S,4S,6S,7R,8R,10R)-7,8-dihydroxy-15-oxo-5-oxatetracyclo[8.4.1.0(1,6).0(4,6)]pentadecane-8-carboxylate | C16H22O6 | 详情 | 详情 | |
| (VII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (VIII) | 30282 | methyl (1S,6R,8R,9S,11R,13R,16S)-8,16-dihydroxy-11-(4-methoxyphenyl)-17-oxo-10,12-dioxatetracyclo[7.6.1.1(1,6).0(13,16)]heptadecane-8-carboxylate | C24H30O8 | 详情 | 详情 | |
| (IX) | 30283 | (1S,6R,8S,9R,11S,13R,16S)-8-([[tert-butyl(diphenyl)silyl]oxy]methyl)-8,16-dihydroxy-11-(4-methoxyphenyl)-10,12-dioxatetracyclo[7.6.1.1(1,6).0(13,16)]heptadecan-17-one | C39H48O7Si | 详情 | 详情 | |
| (X) | 30284 | (1S,4R,6R,8S,9S,13S,15R)-13-([[tert-butyl(diphenyl)silyl]oxy]methyl)-6-(4-methoxyphenyl)-5,7,10,12-tetraoxa-11lambda(4)-thiapentacyclo[13.4.1.0(1,9).0(4,9).0(8,13)]icosane-11,20-dione | C39H46O8SSi | 详情 | 详情 | |
| (XI) | 30285 | (1S,4R,6R,8S,9S,13S,15R)-13-([[tert-butyl(diphenyl)silyl]oxy]methyl)-6-(4-methoxyphenyl)-5,7,10,12-tetraoxa-11lambda(6)-thiapentacyclo[13.4.1.0(1,9).0(4,9).0(8,13)]icosane-11,11,20-trione | C39H46O9SSi | 详情 | 详情 |
合成路线9
该中间体在本合成路线中的序号：(XIII)The chiral diol (XII) is converted to the dioxane derivative (XIV) by treatment with anisaldehyde dimethyl acetal (XIII) in the presence of p-toluenesulfonic acid. Reductive cleavage of dioxane (XIV) by means of DIBAL produces regioselectively the mono-p-methoxybenzyl ether (XV). The primary alcohol group of (XV) is then converted to the corresponding mesylate (XVI) employing methanesulfonyl chloride and triethylamine. Alkylation of the protected glucosamine (XVII) with mesylate (XVI) in the presence of NaH yields ether (XVIII). After basic hydrolysis of the trifluoroacetamide (XVIII), the resultant amine (XIX) is reprotected as the trichloroethyl carbamate (XX) by using trichloroethyl chloroformate and NaHCO3. Subsequent hydrolysis of the acetonide group of (XX) provides diol (XXI).
| 【1】 Nishijima, M.; Kurakata, S.-I.; Shiozaki, M.; Mochizuki, T.; Kanai, S.; Watanabe, Y.; Synthesis of lipid A type pyran carboxylic acids with ether chains and their biological activities. Carbohydr Res 2001, 333, 3, 203. |
| 【2】 Shiozaki, M.; Kurakata, S.; Kanai, S.; Kazama, Y. (Sankyo Co., Ltd.); Ether type lipid A1-carboxylic acid analogues. EP 1152007; JP 2000297096; US 2002161221; US 6511965; WO 0047595 . |
| 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) | 57536 | (3R)-1,3-tetradecanediol | C14H30O2 | 详情 | 详情 | |
| (XIII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XIV) | 57537 | (4R)-2-(4-methoxyphenyl)-4-undecyl-1,3-dioxane; methyl 4-[(4R)-4-undecyl-1,3-dioxan-2-yl]phenyl ether | C22H36O3 | 详情 | 详情 | |
| (XV) | 57538 | (3R)-3-[(4-methoxybenzyl)oxy]-1-tetradecanol | C22H38O3 | 详情 | 详情 | |
| (XVI) | 57539 | (3R)-3-[(4-methoxybenzyl)oxy]tetradecyl methanesulfonate | C23H40O5S | 详情 | 详情 | |
| (XVII) | 57540 | N-[(4aR,6S,7R,8R,8aS)-6-(allyloxy)-8-hydroxy-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-yl]-2,2,2-trifluoroacetamide | C14H20F3NO6 | 详情 | 详情 | |
| (XVIII) | 57541 | N-((4aR,6S,7R,8R,8aS)-6-(allyloxy)-8-{[(3R)-3-(2-[1,1'-biphenyl]-4-ylethoxy)tetradecyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-yl)-2,2,2-trifluoroacetamide | C42H60F3NO7 | 详情 | 详情 | |
| (XIX) | 57542 | (4aR,6S,7R,8R,8aS)-6-(allyloxy)-8-{[(3R)-3-(2-[1,1'-biphenyl]-4-ylethoxy)tetradecyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-amine; (4aR,6S,7R,8R,8aS)-6-(allyloxy)-8-{[(3R)-3-(2-[1,1'-biphenyl]-4-ylethoxy)tetradecyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-ylamine | C40H61NO6 | 详情 | 详情 | |
| (XX) | 57543 | 2,2,2-trichloroethyl (4aR,6S,7R,8R,8aS)-6-(allyloxy)-8-{[(3R)-3-(2-[1,1'-biphenyl]-4-ylethoxy)tetradecyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-ylcarbamate | C43H62Cl3NO8 | 详情 | 详情 | |
| (XXI) | 57544 | 2,2,2-trichloroethyl (2S,3R,4R,5S,6R)-2-(allyloxy)-4-{[(3R)-3-(2-[1,1'-biphenyl]-4-ylethoxy)tetradecyl]oxy}-5-hydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-3-ylcarbamate | C40H58Cl3NO8 | 详情 | 详情 |
合成路线10
该中间体在本合成路线中的序号：(XVIII)The oxidation of the lactol (XIII) with Br2 and BaCO3 gives the lactone (XIV), which is stereoselectively alkylated with allyl bromide (XV) by means of LDA in HMPA to yield lactone (XVI). The opening of the lactone ring of (XVI) with MeONa affords the dihydroxyester (XVII), which is protected by reaction with anisaldehyde dimethylacetal (XVIII) and CSA to provide the benzylidene derivative (XIX). The reduction of the ester group of (XIX) with LiAlH4 gives the corresponding carbinol (XX), which is acylated with Ms-Cl and TEA to yield the mesylate (XXI). The reduction of the mesyloxy group of (XXI) with LiAlH4 affords the dimethyl compound (XXII), which is submitted to a regioselective cleavage of the Pmp protecting group by means of DIBAL in toluene to provide the primary alcohol (XXIII). The oxidation of (XXIII) with DMP gives the corresponding aldehyde (XXIV), which is condensed with tert-butyl isobutyrylacetate (XXV) by means of NaH and BuLi to yield the unsaturated ketoester (XXVI). Stereoselective reduction of the beta-oxo group of (XXVI) by means of Me4NBH(OAc)3 affords the desired diol (XXVII), which is regioselectively silylated at the beta-hydroxy group by means of Tbdms-OTf to provide the monosilyl ether (XXVIII). The oxidation of the remaining hydroxy group of (XXVIII) by means of DMP gives the unsaturated ketoester (XXIX).
| 【1】 Wong, C.-H.; Liu, J.; Aldolase-catalyzed asymmetric synthesis of novel pyranose synthons as a new entry to heterocycles and epothilones. Angew Chem. Int Ed 2002, 41, 8, 1404. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIII) | 54267 | (4S,5S)-5-methyltetrahydro-2H-pyran-2,4-diol | C6H12O3 | 详情 | 详情 | |
| (XIV) | 54268 | (4S,5S)-4-hydroxy-5-methyltetrahydro-2H-pyran-2-one | C6H10O3 | 详情 | 详情 | |
| (XV) | 11463 | 3-Bromo-1-propene; 3-Bromopropene；allyl bromide | 106-95-6 | C3H5Br | 详情 | 详情 |
| (XVI) | 54269 | (3S,4R,5S)-3-allyl-4-hydroxy-5-methyltetrahydro-2H-pyran-2-one | C9H14O3 | 详情 | 详情 | |
| (XVII) | 54270 | methyl (2S)-2-[(1R,2S)-1,3-dihydroxy-2-methylpropyl]-4-pentenoate | C10H18O4 | 详情 | 详情 | |
| (XVIII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (XIX) | 54271 | methyl (2S)-2-[(4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-4-pentenoate | n/a | C18H24O5 | 详情 | 详情 |
| (XX) | 54272 | (2R)-2-[(4S,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-4-penten-1-ol | n/a | C17H24O4 | 详情 | 详情 |
| (XXI) | 54273 | (2R)-2-[(4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-4-pentenyl methanesulfonate | n/a | C18H26O6S | 详情 | 详情 |
| (XXII) | 54274 | (4S,5S)-2-(4-methoxyphenyl)-5-methyl-4-[(1S)-1-methyl-3-butenyl]-1,3-dioxane; methyl 4-{(4S,5S)-5-methyl-4-[(1S)-1-methyl-3-butenyl]-1,3-dioxan-2-yl}phenyl ether | n/a | C17H24O3 | 详情 | 详情 |
| (XXIII) | 54275 | (2S,3S,4S)-3-[(4-methoxybenzyl)oxy]-2,4-dimethyl-6-hepten-1-ol | n/a | C17H26O3 | 详情 | 详情 |
| (XXIV) | 54276 | (2R,3S,4S)-3-[(4-methoxybenzyl)oxy]-2,4-dimethyl-6-heptenal | n/a | C17H24O3 | 详情 | 详情 |
| (XXV) | 54277 | tert-butyl 4-methyl-3-oxopentanoate | 94250-54-1 | C10H18O3 | 详情 | 详情 |
| (XXVI) | 54278 | tert-butyl (5S,6S,7S,8S)-5-hydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-3-oxo-10-undecenoate | n/a | C27H42O6 | 详情 | 详情 |
| (XXVII) | 54279 | tert-butyl (3S,5S,6S,7S,8S)-3,5-dihydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-10-undecenoate | n/a | C27H44O6 | 详情 | 详情 |
| (XXVIII) | 54280 | tert-butyl (3S,5S,6S,7S,8S)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-hydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-10-undecenoate | n/a | C33H58O6Si | 详情 | 详情 |
| (XXIX) | 54281 | tert-butyl (3S,6R,7S,8S)-3-{[tert-butyl(dimethyl)silyl]oxy}-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-5-oxo-10-undecenoate | n/a | C33H56O6Si | 详情 | 详情 |
合成路线11
该中间体在本合成路线中的序号：(VI)Protection of (S)-3-hydroxy-2-methylpropionic acid methyl ester (I) as the corresponding silyl ether, followed by reduction with DIBAL provides the aldehyde (II). Diastereoselective aldol condensation of (II) with the chiral N-propionyl oxazolidinone (III) in the presence of dibutylboron triflate leads to adduct (IV), which is then reduced with LiBH4 to give the diol (V). The diol (V) is protected as the cyclic ketal (VII) by treatment with anisaldehyde dimethylacetal (VI) in the presence of pyridinium p-toluenesulfonate (PPTS). Desilylation of (VII) using tetrabutylammonium fluoride yields the alcohol (VIII). Subsequent iodination of (VIII) with I2/PPh3, followed by displacement of alkyl iodide (IX) with PPh3 in refluxing benzene, furnishes the phosphonium salt (X).
| 【1】 Choy, N.; Shin, Y.; Nguyen, P.Q.; Curran, D.P.; Balachandran, R.; Madiraju, C.; Day, B.W.; Simplified discodermolide analogues: Synthesis and biological evaluation of 4-epi-7-dehydroxy-14,16-didemethyl-(+)-discodermolides as microtubule-stabilizing agents. J Med Chem 2003, 46, 14, 2846. |
| 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) | 17128 | Methyl (2S)-3-hydroxy-2-methylpropanoate | 72657-23-9 | C5H10O3 | 详情 | 详情 |
| (II) | 42624 | (2S)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-methylpropanal | C10H22O2Si | 详情 | 详情 | |
| (III) | 25713 | (4S)-4-benzyl-3-propionyl-1,3-oxazolidin-2-one | C13H15NO3 | 详情 | 详情 | |
| (IV) | 64732 | 3-(5-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-3-hydroxy-2,4-dimethylpentanoyl)-4-(phenylmethyl)-1,3-oxazolidin-2-one | C23H37NO5Si | 详情 | 详情 | |
| (V) | 64733 | 5-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-2,4-dimethyl-1,3-pentanediol | C13H30O3Si | 详情 | 详情 | |
| (VI) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (VII) | 64734 | (1,1-dimethylethyl)(dimethyl)[(2-{5-methyl-2-[4-(methyloxy)phenyl]-1,3-dioxan-4-yl}propyl)oxy]silane; (1,1-dimethylethyl)(dimethyl)silyl 2-{5-methyl-2-[4-(methyloxy)phenyl]-1,3-dioxan-4-yl}propyl ether | C21H36O4Si | 详情 | 详情 | |
| (VIII) | 64735 | 2-{5-methyl-2-[4-(methyloxy)phenyl]-1,3-dioxan-4-yl}-1-propanol | C15H22O4 | 详情 | 详情 | |
| (IX) | 64736 | 4-(2-iodo-1-methylethyl)-5-methyl-2-[4-(methyloxy)phenyl]-1,3-dioxane; 4-[4-(2-iodo-1-methylethyl)-5-methyl-1,3-dioxan-2-yl]phenyl methyl ether | C15H21IO3 | 详情 | 详情 | |
| (X) | 64737 | (2-{5-methyl-2-[4-(methyloxy)phenyl]-1,3-dioxan-4-yl}propyl)(triphenyl)phosphonium iodide | C33H36IO3P | 详情 | 详情 |