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【结 构 式】 
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【分子编号】52860 【品名】(3aS,4S,5R,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-5-formyl-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl acetate 【CA登记号】 |
【 分 子 式 】C20H30O5 【 分 子 量 】350.4552 【元素组成】C 68.55% H 8.63% O 22.83% |
合成路线1
该中间体在本合成路线中的序号：(XXXIII)The synthesis of the racemic fumagillol (+/-)-(XXII) has also been reported. Regioselective dihydroxylation of 1,3-cyclohexadiene-1-carbaldehyde (XXIV) using N-methylmorpholine-N-oxide in the presence of a catalytic amount of OsO4 afforded the cis-diol (XXV), which was further protected as the isopropylidene ketal (XXVI). Conjugate addition to (XXVI) of the organocuprate reagent derived from vinyl bromide (XXVII) in the presence of BF3·Et2O produced (XXVIII) as a mixture of epimers at C-1, which were used without separation. Aldehyde (XXVIII) was converted to the cyclohexyl nitrone (XXX) upon treatment with N-cyclohexyl hydroxylamine (XXIX) and NaHCO-3. Acetylation of (XXX) produced a transitory N-vinyl-O-acetylhydroxylamine (XXXI) which underwent a [3,3] sigmatropic rearrangement to the alpha-acetoxy-N-cyclohexylimine (XXXII). Selective hydrolysis of the imine function of (XXXII) using HOAc/NaOAc furnished aldehyde (XXXIII). This was reduced with LiAlH4, followed by acidic hydrolysis of the isopropylidene ketal to yield the tetraol (XXXIV).
| 【1】 Vosburg, D.A.; et al.; A concise synthesis of fumagillol. Angew Chem. Int Ed 1999, 38, 7, 971. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXVIIIIa) | 52854 | (3aS,4S,5R,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxole-5-carbaldehyde | C18H28O3 | 详情 | 详情 | |
| (XXVIIIIb) | 52855 | (3aS,4S,5S,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxole-5-carbaldehyde | C18H28O3 | 详情 | 详情 | |
| (XXIV) | 52850 | 1,3-cyclohexadiene-1-carbaldehyde | C7H8O | 详情 | 详情 | |
| (XXV) | 52851 | (3S,4R)-3,4-dihydroxy-1-cyclohexene-1-carbaldehyde | C7H10O3 | 详情 | 详情 | |
| (XXVI) | 52852 | (3aS,7aR)-2,2-dimethyl-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carbaldehyde | C10H14O3 | 详情 | 详情 | |
| (XXVII) | 52853 | (2E)-2-bromo-6-methyl-2,5-heptadiene | C8H13Br | 详情 | 详情 | |
| (XXIX) | 52856 | N-Cyclohexylhydroxylamine | C6H13NO | 详情 | 详情 | |
| (XXX) | 52857 | ((Z)-{(3aS,4S,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl}methylidene)(cyclohexyl)ammoniumolate | C24H39NO3 | 详情 | 详情 | |
| (XXXI) | 52858 | (3aS,4R,7aR)-5-{(E)-[(acetyloxy)(cyclohexyl)amino]methylidene}-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxole | C26H41NO4 | 详情 | 详情 | |
| (XXXII) | 52859 | (3aS,4S,5R,7aR)-5-[(cyclohexylimino)methyl]-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl acetate | C26H41NO4 | 详情 | 详情 | |
| (XXXIII) | 52860 | (3aS,4S,5R,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-5-formyl-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl acetate | C20H30O5 | 详情 | 详情 | |
| (XXXIV) | 52861 | (1R,2S,3S,4R)-3-[(1E)-1,5-dimethyl-1,4-hexadienyl]-4-(hydroxymethyl)-1,2,4-cyclohexanetriol | C15H26O4 | 详情 | 详情 |