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【结 构 式】 
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【分子编号】64599 【品名】(1R,2R,3S)-2-(benzyloxy)-1-[(1R)-1,2-dihydroxyethyl]-3-methyl-4-pentenyl benzoate 【CA登记号】 |
【 分 子 式 】C22H26O5 【 分 子 量 】370.44544 【元素组成】C 71.33% H 7.07% O 21.59% |
合成路线1
该中间体在本合成路线中的序号：(VI)Tetrahydropyran intermediate (X). The asymmetric addition of Ipc2B-crotyl to 4-(Tbdps-O)-2-butenal (I) gives the chiral secondary alcohol (II), which is protected with benzyl bromide and NaH to yield the benzyl ether (III). The desilylation of (III) by means of TBAF affords the primary alcohol (IV), which is submitted to a Sharpless asymmetric epoxidation to provide the epoxide (V). Ring opening of (V) by means of Ti(iPrO)4 and benzoic acid gives the benzoate ester (VI), which is cyclized by means of Hg(OAc)2 to yield the tetrahydropyran derivative (VII). Hydrolysis of the benzoate group of (VII) by means of MeONa affords the trihydroxy compound (VIII), which is treated with acetone and Ts-OH to provide the acetonide (IX). Finally, oxidation of the hydroxymethyl group of (IX) by means of Swern oxidant yields the target tetrahydropyran-2-carbaldehyde intermediate (X).
| 【1】 Smith, A.B. III; Zhuang, L.; Brook, C.S.; Boldi, A.M.; McBriar, M.D.; Moser, W.H.; Murase, N.; Nakayama, K.; Verhoest, P.R.; Lin, Q.; Spongistatin synthetic studies. 1. Construction of a C(29-48) subtarget. Tetrahedron Lett 1997, 38, 50, 8667. |
| 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) | 60351 | 4-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-2-butenal | C20H24O2Si | 详情 | 详情 | |
| (II) | 64595 | (3S,4R,5E)-7-{[tert-butyl(diphenyl)silyl]oxy}-3-methyl-1,5-heptadien-4-ol | C24H32O2Si | 详情 | 详情 | |
| (III) | 64596 | benzyl (1R,2E)-4-{[tert-butyl(diphenyl)silyl]oxy}-1-[(1S)-1-methyl-2-propenyl]-2-butenyl ether; {[(2E,4R,5S)-4-(benzyloxy)-5-methyl-2,6-heptadienyl]oxy}(tert-butyl)diphenylsilane | C31H38O2Si | 详情 | 详情 | |
| (IV) | 64597 | (2E,4R,5S)-4-(benzyloxy)-5-methyl-2,6-heptadien-1-ol | C15H20O2 | 详情 | 详情 | |
| (V) | 54598 | tert-butyl (1S,2R)-1-(sec-butyl)-2-methoxy-4-pentenyl(methyl)carbamate | C16H31NO3 | 详情 | 详情 | |
| (VI) | 64599 | (1R,2R,3S)-2-(benzyloxy)-1-[(1R)-1,2-dihydroxyethyl]-3-methyl-4-pentenyl benzoate | C22H26O5 | 详情 | 详情 | |
| (VII) | 64600 | (2R,3S,4R,5R)-2-[(acetyloxy)methyl]-4-(benzyloxy)-6-(hydroxymethyl)-5-methyltetrahydro-2H-pyran-3-yl benzoate | C24H28O7 | 详情 | 详情 | |
| (VIII) | 64601 | (2R,3S,4R,5R)-4-(benzyloxy)-2,6-bis(hydroxymethyl)-5-methyltetrahydro-2H-pyran-3-ol | C15H22O5 | 详情 | 详情 | |
| (IX) | 64602 | [(4aR,7R,8R,8aS)-8-(benzyloxy)-2,2,7-trimethylhexahydropyrano[3,2-d][1,3]dioxin-6-yl]methanol | C18H26O5 | 详情 | 详情 | |
| (X) | 64603 | (4aR,7R,8R,8aS)-8-(benzyloxy)-2,2,7-trimethylhexahydropyrano[3,2-d][1,3]dioxine-6-carbaldehyde | C18H24O5 | 详情 | 详情 |