• English
  • 简体中文
Login Register
Current Location: Home > Feedback Help Print

【结 构 式】

【分子编号】64651

【品名】(2S,3R,4S,5R)-5-[(benzyloxy)methoxy]-6-((2S,4S,6R,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-1-[((2R,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-methoxy-4-methyltetrahydro-2H-pyran-2-yl)methyl]-3-[(2,4-dimethoxybenzyl)oxy]-2,4-dimethylhexyl phenyl sulfone; ({(2R,4S,6R,8S,10S)-8-[(2R,3S,4R,5S)-2-[(benzyloxy)methoxy]-7-((2R,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-methoxy-4-methyltetrahydro-2H-pyran-2-yl)-4-[(2,4-dimethoxybenzyl)oxy]-3,5-dimethyl-6-(phenylsulfonyl)heptyl]-2-[(benzyloxy)methyl]-10-methoxy-1,7-dioxaspiro[5.5]undec-4-yl}oxy)(tert-butyl)dimethylsilane

【CA登记号】

【 分 子 式 】C94H140O18SSi3

【 分 子 量 】1674.4573

【元素组成】C 67.43% H 8.43% O 17.2% S 1.92% Si 5.03%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(LXIV)

Assembly of the target compound. The condensation of the iodomethyl tetrahydropyran intermediate (XLVII) with the spiranic phenylsulfone derivative (LXIII) by means of BuLi in toluene gives the adduct (LXIV), which is desulfurized by methylenation with CH2I2 and i-PrMgCl in THF/HMPA to yield (LXV). The reaction of (LXV) with TBAF, followed by selective resilylation with Tbdms-Cl and imidazole and cleavage of the acetonide group with concomitant spiroketalization by means of HClO4 affords the bis spiroketal compound (LXVI). The cleavage of the benzyl ether group of (LXVI) by means of DDQ, followed by selective acetylation of the secondary OH group provides acetate (LXVII), which is silylated with Tes-OTf and lutidine, and selectively deprotected by means of HF and pyridine to give the primary alcohol (LXVIII). The oxidation of (LXVIII) with DMP and NaClO2, followed by silylation with Tips-Cl and TEA yields the silyl ester (LXIX).

1 Smith, A.B.; et al.; The spongistatins: Architecturally complex natural products - Part one: A formal synthesis of (+)-spongistatin 1 by construction of an advanced ABCD fragment. Angew Chem. Int Ed 2001, 40, 1, 191.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XLVII) 64635 tert-butyl(dimethyl)silyl (2R,4S,6R)-2-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-(iodomethyl)-2-methoxy-4-methyltetrahydro-2H-pyran-4-yl ether; tert-butyl[2-((4S,6S)-6-{[(2R,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(iodomethyl)-2-methoxy-4-methyltetrahydro-2H-pyran-2-yl]methyl}-2,2-dimethyl-1,3-dioxan-4-yl)ethoxy]diphenylsilane C39H63IO6Si2 详情 详情
(LXIII) 64650 (2S,3R,4S,5R)-5-[(benzyloxy)methoxy]-6-((2S,4S,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-3-[(2,4-dimethoxybenzyl)oxy]-2,4-dimethylhexyl phenyl sulfone; ({(2R,4S,8S,10S)-8-[(2R,3S,4R,5S)-2-[(benzyloxy)methoxy]-4-[(2,4-dimethoxybenzyl)oxy]-3,5-dimethyl-6-(phenylsulfonyl)hexyl]-2-[(benzyloxy)methyl]-10-methoxy-1,7-dioxaspiro[5.5]undec-4-yl}oxy)(tert-butyl)dimethylsilane C55H78O12SSi 详情 详情
(LXIV) 64651 (2S,3R,4S,5R)-5-[(benzyloxy)methoxy]-6-((2S,4S,6R,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-1-[((2R,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-methoxy-4-methyltetrahydro-2H-pyran-2-yl)methyl]-3-[(2,4-dimethoxybenzyl)oxy]-2,4-dimethylhexyl phenyl sulfone; ({(2R,4S,6R,8S,10S)-8-[(2R,3S,4R,5S)-2-[(benzyloxy)methoxy]-7-((2R,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-methoxy-4-methyltetrahydro-2H-pyran-2-yl)-4-[(2,4-dimethoxybenzyl)oxy]-3,5-dimethyl-6-(phenylsulfonyl)heptyl]-2-[(benzyloxy)methyl]-10-methoxy-1,7-dioxaspiro[5.5]undec-4-yl}oxy)(tert-butyl)dimethylsilane C94H140O18SSi3 详情 详情
(LXV) 64652 ({(2R,4S,8S,10S)-8-{(2R,3S,4S,5R)-2-[(benzyloxy)methoxy]-6-[((2S,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-methoxy-4-methyltetrahydro-2H-pyran-2-yl)methyl]-4-[(2,4-dimethoxybenzyl)oxy]-3,5-dimethyl-6-heptenyl}-2-[(benzyloxy)methyl]-10-methoxy-1,7-dioxaspiro[5.5]undec-4-yl}oxy)(tert-butyl)dimethylsilane; benzyl ((2R,4S,8S,10S)-8-{(2R,3S,4S,5R)-2-[(benzyloxy)methoxy]-6-[((2S,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{[(4S,6S)-6-(2-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-2,2-dimethyl-1,3-dioxan-4-yl]methyl}-6-methoxy-4-methyltetrahydro-2H-pyran-2-yl)methyl]-4-[(2,4-dimethoxybenzyl)oxy]-3,5-dimethyl-6-heptenyl}-4-{[tert-butyl(dimethyl)silyl]oxy}-10-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)methyl ether C89H136O16Si3 详情 详情
(LXVI) 64653 (2S,4S,6R,8S,10S)-2-(2-{(1R,2S,3S,4R)-4-[(benzyloxy)methoxy]-5-((2S,4S,6S,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-2-[(2,4-dimethoxybenzyl)oxy]-1,3-dimethylpentyl}-2-propenyl)-10-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-4-methyl-1-oxaspiro[5.5]undecane-4,8-diol C70H112O14Si2 详情 详情
(LXVII) 64654 (2S,4S,6R,8S,10S)-2-{2-[(1R,2S,3R,4R)-2-(acetyloxy)-4-[(benzyloxy)methoxy]-5-((2S,4S,6S,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-1,3-dimethylpentyl]-2-propenyl}-10-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-4-hydroxy-4-methyl-1-oxaspiro[5.5]undec-8-yl acetate C65H106O14Si2 详情 详情
(LXVIII) 64655 (2S,4S,6R,8S,10S)-2-{2-[(1R,2S,3R,4R)-2-(acetyloxy)-4-[(benzyloxy)methoxy]-5-((2S,4S,6S,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-1,3-dimethylpentyl]-2-propenyl}-10-(2-hydroxyethyl)-4-methyl-4-[(triethylsilyl)oxy]-1-oxaspiro[5.5]undec-8-yl acetate C65H106O14Si2 详情 详情
(LXIX) 64656 triisopropylsilyl 2-{(2S,4S,6R,8S,10S)-10-(acetyloxy)-2-{2-[(1R,2S,3R,4R)-2-(acetyloxy)-4-[(benzyloxy)methoxy]-5-((2S,4S,8R,10S)-8-[(benzyloxy)methyl]-10-{[tert-butyl(dimethyl)silyl]oxy}-4-methoxy-1,7-dioxaspiro[5.5]undec-2-yl)-1,3-dimethylpentyl]-2-propenyl}-4-methyl-4-[(triethylsilyl)oxy]-1-oxaspiro[5.5]undec-8-yl}acetate C74H124O15Si3 详情 详情
Extended Information