【结 构 式】 |
【分子编号】42583 【品名】1-[(2R,5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3-(phenylsulfonyl)-2,5-dihydro-2-furanyl]-5-methyl-2,4(1H,3H)-pyrimidinedione 【CA登记号】 |
【 分 子 式 】C32H34N2O6SSi 【 分 子 量 】602.78334 【元素组成】C 63.76% H 5.69% N 4.65% O 15.93% S 5.32% Si 4.66% |
合成路线1
该中间体在本合成路线中的序号:(X)The reaction of gamma-lactone (I) with N-(phenylsulfanyl)phthalimide (II) by means of LiHMDS in THF gives the 2,2-bis(phenylsulfanyl)lactone (III), which is reduced with DIBAL in THF to yield 5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-2,2-bis(phenylsulfanyl)-D-ribose (IV). The reaction of (IV) with acetic anhydride affords the acetylated ribose (V), which is condensed with bis(trimethylsilyl)thymine (VI) by means of TMS-OTf in acetonitrile to provide the glycosylated thymine (VII). The oxidation of (VII) with 1 mol of MCPBA in dichloromethane gives the sulfinyl compound (VIII), which is treated with tributylamine in refluxing xylene to yield the 2',3'-didehydro compound (IX). The oxidation of (IX) with MCPBA in dichloromethane gives the phenylsulfonyl derivative (X), which is desulfurized with sodium amalgam in methanol, yielding the silylated intermediate (XI). Finally, this compound is desilylated with TBAF in THF.
【1】 Kawakami, H.; et al.; Condensation reaction between 2,2-diphenylthio-2,3-dideoxyriboside and silyvated pyrimidine bases. Nucleosides Nucleotides 1992, 11, 9, 1673. |
【2】 Ebata, T.; Matsushita, H.; Kuno, H.; Niihata, S.; Synthesis of 2',3'-didehydro-2',3'-dideoxy nucleosides from 2',2'-bis (phenylthio) nucleoside analogs. Bull Chem Soc Jpn 1995, 68, 8, 2327. |
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) | 12215 | (5S)-5-([[tert-Butyl(diphenyl)silyl]oxy]methyl)dihydro-2(3H)-furanone | C21H26O3Si | 详情 | 详情 | |
(II) | 42577 | 2-(phenylsulfanyl)-1H-isoindole-1,3(2H)-dione | 14204-27-4 | C14H9NO2S | 详情 | 详情 |
(III) | 42578 | (5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3,3-bis(phenylsulfanyl)dihydro-2(3H)-furanone | C33H34O3S2Si | 详情 | 详情 | |
(IV) | 42579 | (5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3,3-bis(phenylsulfanyl)tetrahydro-2-furanol | C33H36O3S2Si | 详情 | 详情 | |
(V) | 42580 | (5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3,3-bis(phenylsulfanyl)tetrahydro-2-furanyl acetate | C35H38O4S2Si | 详情 | 详情 | |
(VI) | 41900 | 5-methyl-2,4-bis[(trimethylsilyl)oxy]pyrimidine; 5-methyl-2-[(trimethylsilyl)oxy]-4-pyrimidinyl trimethylsilyl ether | 7288-28-0 | C11H22N2O2Si2 | 详情 | 详情 |
(VII) | 42584 | 1-[(2S,5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3,3-bis(phenylsulfanyl)tetrahydro-2-furanyl]-5-methyl-2,4(1H,3H)-pyrimidinedione | C38H40N2O4S2Si | 详情 | 详情 | |
(VIII) | 42581 | 1-[(2R,5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3-(phenylsulfanyl)-3-(phenylsulfinyl)tetrahydro-2-furanyl]-5-methyl-2,4(1H,3H)-pyrimidinedione | C38H40N2O5S2Si | 详情 | 详情 | |
(IX) | 42582 | 1-[(2R,5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3-(phenylsulfanyl)-2,5-dihydro-2-furanyl]-5-methyl-2,4(1H,3H)-pyrimidinedione | C32H34N2O4SSi | 详情 | 详情 | |
(X) | 42583 | 1-[(2R,5S)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-3-(phenylsulfonyl)-2,5-dihydro-2-furanyl]-5-methyl-2,4(1H,3H)-pyrimidinedione | C32H34N2O6SSi | 详情 | 详情 | |
(XI) | 12223 | 1-[(2R,5S)-5-([[tert-Butyl(diphenyl)silyl]oxy]methyl)-2,5-dihydro-2-furanyl]-5-methyl-2,4(1H,3H)-pyrimidinedione | C26H30N2O4Si | 详情 | 详情 |