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【结 构 式】

【分子编号】47374

【品名】dimethyl (4R,5R)-2-phenyl-1,3-dioxolane-4,5-dicarboxylate

【CA登记号】38270-72-3

【 分 子 式 】C13H14O6

【 分 子 量 】266.25056

【元素组成】C 58.65% H 5.3% O 36.05%

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:(II)

Synthesis of oxazolidine intermediate (XVI): The reaction of dimethyl L-tartrate (I) with benzaldehyde and Ts-OH gives the benzylidene ketal (II), which is reduced with LiAlH4/AlCl3 to yield the monobenzylated tetrol (III). The reaction of (III) with 2,2-dimethoxypropane (IV) and TsOH affords the acetonide (V), which is protected at the primary OH group with Mpm-Cl and NaH to provide the corresponding ether (VI). The debenzylation of (VI) with H2 over Raney-Ni in ethanol, followed by reaction with MsCl and TEA in dichloromethane, gives the mesylate (VII), which is treated with HCl in methanol to yield the diol (VIII). The reaction of (VIII) with K2CO3 in methanol affords the epoxide (IX), which is opened with NaN3 in refluxing ethanol to provide the azide (X). The selective monosilylation of (X) with Tbdps-Cl, TEA and DMAP in dichloromethane furnishes the silyl ether (XI). The reduction of the azido group of (XI) with PPh3 in THF/water gives the amine (XII), which is protected with Troc-Cl and NaHCO3 to afford the carbamate (XIII). The reaction of (XIII) with 2,2-dimethoxypropane (IV) and TsOH provides the oxazolidine (XIV), which is selectively deprotected at the Mpm group with DDQ in dichloromethane, giving the primary alcohol (XV). Finally, this compound is esterified with Tf2O and TEA in CH2Cl2 to obtain the desired oxazolidine intermediate (XVI).

1 Al-Hakim, A.H.; et al.; Synthesis of 1,2-O-isopropylidene-L-threitol and its conversion to (R)-1,2-O-isopropylideneglycerol. Synthesis 1985, 207.
2 Katoh, T.; Terashima, S.; Total synthesis of antitumor antibiotic FR900482. Yuki Gosei Kagaku Kyokaishi 1997, 55, 11, 946.
3 Ohno, M.; et al.; An enantioselective synthesis of platelet-activating factors, their enantiomers, and their analogues from D- and L-tartaric acids. Chem Pharm Bull 1985, 33, 2, 572.
4 Yoshino, T.; et al.; Total synthesis of natural (+)-FR900482. 2. Efficient syntheses of the aromatic and the optically active aliphatic fragments. Tetrahedron Lett 1996, 37, 20, 3475.
5 Yoshino, T.; et al.; Total synthesis of an enantiomeric pair of FR900482. 2. Syntheses of the aromatic and the optically active aliphatic segments. Tetrahedron 1997, 53, 30, 10239.
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) 28476 dimethyl (2S,3S)-2,3-dimethylbutanedioate C6H10O6 详情 详情
(II) 47374 dimethyl (4R,5R)-2-phenyl-1,3-dioxolane-4,5-dicarboxylate 38270-72-3 C13H14O6 详情 详情
(III) 43826 (2S,3S)-3-(benzyloxy)-1,2,4-butanetriol C11H16O4 详情 详情
(IV) 10722 1-Methoxy-1-methylethyl methyl ether; 2,2-Dimethoxypropane 77-76-9 C5H12O2 详情 详情
(V) 47375 (2S)-2-(benzyloxy)-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-ethanol C14H20O4 详情 详情
(VI) 47376 (4S)-4-[(1S)-1-(benzyloxy)-2-[(4-methoxybenzyl)oxy]ethyl]-2,2-dimethyl-1,3-dioxolane; benzyl (1S)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-[(4-methoxybenzyl)oxy]ethyl ether C22H28O5 详情 详情
(VII) 47377 (1S)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-[(4-methoxybenzyl)oxy]ethyl methanesulfonate C16H24O7S 详情 详情
(VIII) 47378 (1S,2S)-2,3-dihydroxy-1-[[(4-methoxybenzyl)oxy]methyl]propyl methanesulfonate C13H20O7S 详情 详情
(IX) 47379 ((2S,3R)-3-[[(4-methoxybenzyl)oxy]methyl]oxiranyl)methanol C12H16O4 详情 详情
(X) 47380 (2R,3S)-2-azido-4-[(4-methoxybenzyl)oxy]-1,3-butanediol C12H17N3O4 详情 详情
(XI) 47381 (2S,3R)-3-azido-4-[[tert-butyl(diphenyl)silyl]oxy]-1-[(4-methoxybenzyl)oxy]-2-butanol C28H35N3O4Si 详情 详情
(XII) 47382 (2S,3R)-3-amino-4-[[tert-butyl(diphenyl)silyl]oxy]-1-[(4-methoxybenzyl)oxy]-2-butanol C28H37NO4Si 详情 详情
(XIII) 47383 2,2,2-trichloroethyl (1R,2S)-1-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2-hydroxy-3-[(4-methoxybenzyl)oxy]propylcarbamate C31H38Cl3NO6Si 详情 详情
(XIV) 47384 2,2,2-trichloroethyl (4R)-4-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-[[(4-methoxybenzyl)oxy]methyl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate C34H42Cl3NO6Si 详情 详情
(XV) 47385 2,2,2-trichloroethyl (4R)-4-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-(hydroxymethyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate C26H34Cl3NO5Si 详情 详情
(XVI) 47386 2,2,2-trichloroethyl (4R)-4-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2,2-dimethyl-5-([[(trifluoromethyl)sulfonyl]oxy]methyl)-1,3-oxazolidine-3-carboxylate C27H33Cl3F3NO7SSi 详情 详情
Extended Information