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【结 构 式】 
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【分子编号】42776 【品名】methyl (2R,3S,4R,5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18R,19S,20S,21Z)-5-[[tert-butyl(dimethyl)silyl]oxy]-19-hydroxy-3,17-bis[(4-methoxybenzyl)oxy]-7,11-bis(methoxymethoxy)-2,4,10,12,14,16,18,20-octamethyl-8,13,21,23-tetracosatetraenoate 【CA登记号】 |
【 分 子 式 】C59H96O12Si 【 分 子 量 】1025.48954 【元素组成】C 69.1% H 9.44% O 18.72% Si 2.74% |
合成路线1
该中间体在本合成路线中的序号：(XLV)The target compound has been obtained as follows: The condensation of the intermediate iodo compound (XXII) with the intermediate lithium salt (XLI) gives the adduct (XLII), which is treated with iBu2AlH to yield the primary alcohol (XLIII). The oxidation of (XLIII) with DMP and NaClO2, followed by esterification with trimethylsilyldiazomethane affords the methyl ester (XLIV), which is selectively desilylated (elimination of the Tes group) with Ts-OH, providing the secondary alcohol (XLV). The reaction of (XLV) with trichloroacetyl isocyanate gives the corresponding carbamate (XLVI), which is debenzylated with DDQ to afford the precursor. Finally, (XLVII) is fully deprotected with HCl in methanol.
| 【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 |
|---|---|---|---|---|---|---|
| (XXII) | 42755 | (5S,6S,7Z,9S,11S)-5-[(1S,2Z)-3-iodo-1-methyl-2-butenyl]-9-(methoxymethoxy)-11-[(1R)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]-6,13,13,14,14-pentamethyl-2,4,12-trioxa-13-sila-7-pentadecene; tert-butyl(dimethyl)silyl (1S,3S,4Z,6S,7S,8S,9Z)-10-iodo-3,7-bis(methoxymethoxy)-1-[(1R)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]-6,8-dimethyl-4,9-undecadienyl ether | C37H63IO8Si | 详情 | 详情 | |
| (XLI) | 42772 | C36H62BLiO4Si | 详情 | 详情 | ||
| (XLII) | 42773 | (5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18S,19S)-21,21-diethyl-17-[(4-methoxybenzyl)oxy]-7,11-bis(methoxymethoxy)-5-[(1R)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]-2,2,3,3,10,12,14,16,18-nonamethyl-19-[(1S,2Z)-1-methyl-2,4-pentadie; tert-butyl(dimethyl)silyl (1S,3S,4Z,6S,7S,8S,9Z,12S,13R,14S,15S,16S,17Z)-13-[(4-methoxybenzyl)oxy]-3,7-bis(methoxymethoxy)-1-[(1R)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]-6,8,10,12,14,16-hexamethyl-15-[(triethylsilyl)oxy]-4 | C64H108O11Si2 | 详情 | 详情 | |
| (XLIII) | 42774 | (2S,3R,4R,5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18S,19S,20S,21Z)-5-[[tert-butyl(dimethyl)silyl]oxy]-3,17-bis[(4-methoxybenzyl)oxy]-7,11-bis(methoxymethoxy)-2,4,10,12,14,16,18,20-octamethyl-19-[(triethylsilyl)oxy]-8,13,21,23-tetracosatetraen-1-ol | C64H110O11Si2 | 详情 | 详情 | |
| (XLIV) | 42775 | methyl (2R,3S,4R,5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18S,19S,20S,21Z)-5-[[tert-butyl(dimethyl)silyl]oxy]-3,17-bis[(4-methoxybenzyl)oxy]-7,11-bis(methoxymethoxy)-2,4,10,12,14,16,18,20-octamethyl-19-[(triethylsilyl)oxy]-8,13,21,23-tetracosatetraenoate | C65H110O12Si2 | 详情 | 详情 | |
| (XLV) | 42776 | methyl (2R,3S,4R,5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18R,19S,20S,21Z)-5-[[tert-butyl(dimethyl)silyl]oxy]-19-hydroxy-3,17-bis[(4-methoxybenzyl)oxy]-7,11-bis(methoxymethoxy)-2,4,10,12,14,16,18,20-octamethyl-8,13,21,23-tetracosatetraenoate | C59H96O12Si | 详情 | 详情 | |
| (XLVI) | 42777 | methyl (2R,3S,4R,5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18S,19S,20S,21Z)-19-[(aminocarbonyl)oxy]-5-[[tert-butyl(dimethyl)silyl]oxy]-3,17-bis[(4-methoxybenzyl)oxy]-7,11-bis(methoxymethoxy)-2,4,10,12,14,16,18,20-octamethyl-8,13,21,23-tetracosatetraenoate | C60H97NO13Si | 详情 | 详情 | |
| (XLVII) | 42778 | methyl (2R,3S,4R,5S,7S,8Z,10S,11S,12S,13Z,16S,17R,18S,19S,20S,21Z)-19-[(aminocarbonyl)oxy]-5-[[tert-butyl(dimethyl)silyl]oxy]-3,17-dihydroxy-7,11-bis(methoxymethoxy)-2,4,10,12,14,16,18,20-octamethyl-8,13,21,23-tetracosatetraenoate | C44H81NO11Si | 详情 | 详情 |