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【结 构 式】 
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【分子编号】57333 【品名】(4S)-4-[(1S)-1-(1,3-dithian-2-yl)ethyl]-2-(4-methoxyphenyl)-1,3-dioxolane; 4-{(4S)-4-[(1S)-1-(1,3-dithian-2-yl)ethyl]-1,3-dioxolan-2-yl}phenyl methyl ether 【CA登记号】 |
【 分 子 式 】C16H22O3S2 【 分 子 量 】326.48088 【元素组成】C 58.86% H 6.79% O 14.7% S 19.64% |
合成路线1
该中间体在本合成路线中的序号：(VIII)Synthesis of the intermediate butyraldehyde (X): The Sharpless asymmetric epoxidation of 2(E)-buten-1-ol by means of t-Bu-OOH and D-(-9-diisopropyl tartrate gives the epoxy alcohol (II), which is treated with Tbdps-Cl, TEA and DMAP to yield the silyl ether (III) The condensation of (III) with 1,3-dithiane (IV) by means of BuLi in THF/HMPA affords the cyclic thioketal (V), which is deprotected by means of TBAF in THF, affording the diol (VI). The reaction of (VI) with 4-methoxybenzaldehyde dimethylacetal (VII) by means of TsOH in DMF provides the benzylidene ketal (VIII), which is submitted to a selective opening by means of DIBAL in dichloromethane to give the secondary benzyl ether (IX). Finally this compound is oxidized with SO3/Pyridine and TEA in DMSO/dichloromethane to obtain the target intermediate, the chiral butyraldehyde (X).
| 【1】 Chen, K.; Formal total synthesis of (-)-FK506. Diss Abstr Int B - Sci Eng 1993, 53, 9, 4663. |
| 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) | 54882 | 2-Butene-1-ol; Crotyl Alcohol; trans-Propenylcarbinol | 504-61-0 | C4H8O | 详情 | 详情 |
| (II) | 57330 | [(2R,3R)-3-methyloxiranyl]methanol | C4H8O2 | 详情 | 详情 | |
| (III) | 14956 | tert-butyl[[(2R,3R)-3-methyloxiranyl]methoxy]diphenylsilane; tert-butyl(diphenyl)silyl [(2R,3R)-3-methyloxiranyl]methyl ether | C20H26O2Si | 详情 | 详情 | |
| (IV) | 42372 | 1,3-dithiane | 505-23-7 | C4H8S2 | 详情 | 详情 |
| (V) | 57331 | (2S,3S)-1-{[tert-butyl(diphenyl)silyl]oxy}-3-(1,3-dithian-2-yl)-2-butanol | C24H34O2S2Si | 详情 | 详情 | |
| (VI) | 57332 | (2S,3S)-3-(1,3-dithian-2-yl)-1,2-butanediol | C8H16O2S2 | 详情 | 详情 | |
| (VII) | 26485 | 1-(dimethoxymethyl)-4-methoxybenzene | 2186-92-7 | C10H14O3 | 详情 | 详情 |
| (VIII) | 57333 | (4S)-4-[(1S)-1-(1,3-dithian-2-yl)ethyl]-2-(4-methoxyphenyl)-1,3-dioxolane; 4-{(4S)-4-[(1S)-1-(1,3-dithian-2-yl)ethyl]-1,3-dioxolan-2-yl}phenyl methyl ether | C16H22O3S2 | 详情 | 详情 | |
| (IX) | 57334 | (2S,3S)-3-(1,3-dithian-2-yl)-2-[(4-methoxybenzyl)oxy]-1-butanol | C16H24O3S2 | 详情 | 详情 | |
| (X) | 57335 | (2S,3S)-3-(1,3-dithian-2-yl)-2-[(4-methoxybenzyl)oxy]butanal | C16H22O3S2 | 详情 | 详情 |