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【结 构 式】

【分子编号】54278

【品名】tert-butyl (5S,6S,7S,8S)-5-hydroxy-7-[(4-methoxybenzyl)oxy]-4,4,6,8-tetramethyl-3-oxo-10-undecenoate

【CA登记号】n/a

【 分 子 式 】C27H42O6

【 分 子 量 】462.62688

【元素组成】C 70.1% H 9.15% O 20.75%

与该中间体有关的原料药合成路线共 2 条

合成路线1

该中间体在本合成路线中的序号:(XXVI)

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2

该中间体在本合成路线中的序号:(XXVI)

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
Extended Information