【结 构 式】 |
【分子编号】50731 【品名】8-(tert-butoxy)-4a,7,8,8a-tetrahydro-1,4,6(5H)-naphthalenetrione 【CA登记号】 |
【 分 子 式 】C14H18O4 【 分 子 量 】250.29452 【元素组成】C 67.18% H 7.25% O 25.57% |
合成路线1
该中间体在本合成路线中的序号:(IX)The Diels-Alder cyclization of butadiene (VII) with 1,4-benzoquinone (VIII) in THF gives the naphthalenetrione (IX), which is acylated with acetic anhydride and TEA to yield the tetralone derivative (X). The Grignard reaction of (X) with vinylmagnesium bromide (XI) and CeCl3, followed by acylation with acetic anhydride, affords the tetraline derivative (XII), which is treated with NaBH4 and oxidized with cerium ammonium nitrate to provide the tetrahydronaphthoquinone (XIII). The cyclization of (XIII) with 4-acetoxy-3,4-dihydro-1H-2-benzopyran-1,3-dione (XIV) by means of NaH in THF gives the intermediate (XV), which rearranges to the tetracyclic dione (XVI). The palladium-catalyzed (PdCl2(MeCN)2) rearrangement of (XVI) in toluene yields the allyl acetate derivative (XVII), which is oxidized with peracetic acid and RuCl3 in water/acetonitrile/dichloromethane to afford the protected intermediate (XVIII). Finally, this compound is deprotected and simultaneously epimerized by a treatment with HCl in refluxing isopropanol/water to provide the desired target intermediate (II).
【1】 Hottop, T.; et al.; Synthesis of 4-demethoxyadriamycinone utilizing ruthenium-catalyzed oxidation of allyl acetates. Tetrahedron Lett 2001, 42, 19, 3343. |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(II) | 50740 | (7S,9S)-9-glycoloyl-6,7,9,11-tetrahydroxy-7,8,9,10-tetrahydro-5,12-naphthacenedione | C20H16O8 | 详情 | 详情 | |
(VII) | 50730 | [[(E)-3-(tert-butoxy)-1-methylene-2-propenyl]oxy](trimethyl)silane; (E)-3-(tert-butoxy)-1-methylene-2-propenyl trimethylsilyl ether | C11H22O2Si | 详情 | 详情 | |
(VIII) | 12633 | Quinone; Benzo-1,4-quinone; 2,5-Cyclohexadiene-1,4-dione | 106-51-4 | C6H4O2 | 详情 | 详情 |
(IX) | 50731 | 8-(tert-butoxy)-4a,7,8,8a-tetrahydro-1,4,6(5H)-naphthalenetrione | C14H18O4 | 详情 | 详情 | |
(X) | 50732 | 4-(acetoxy)-5-(tert-butoxy)-7-oxo-5,6,7,8-tetrahydro-1-naphthalenyl acetate | C18H22O6 | 详情 | 详情 | |
(XI) | 16524 | bromo(vinyl)magnesium | 1826-67-1 | C2H3BrMg | 详情 | 详情 |
(XII) | 50733 | (2S,4S)-5,8-bis(acetoxy)-4-(tert-butoxy)-2-vinyl-1,2,3,4-tetrahydro-2-naphthalenyl acetate | C22H28O7 | 详情 | 详情 | |
(XIII) | 50734 | (2S,4S)-4-(tert-butoxy)-5,8-dioxo-2-vinyl-1,2,3,4,5,8-hexahydro-2-naphthalenyl acetate | C18H22O5 | 详情 | 详情 | |
(XIV) | 50735 | 1,3-dioxo-3,4-dihydro-1H-isochromen-4-yl acetate | C11H8O5 | 详情 | 详情 | |
(XV) | 50736 | (2S,4S)-6-(acetoxy)-4-(tert-butoxy)-11-hydroxy-5,12-dioxo-2-vinyl-1,2,3,4,5,12-hexahydro-2-naphthacenyl acetate | C28H28O8 | 详情 | 详情 | |
(XVI) | 50737 | (2S,4S)-2-(acetoxy)-4-(tert-butoxy)-12-hydroxy-6,11-dioxo-2-vinyl-1,2,3,4,6,11-hexahydro-5-naphthacenyl acetate | C28H28O8 | 详情 | 详情 | |
(XVII) | 50738 | 2-[5-(acetoxy)-4-(tert-butoxy)-12-hydroxy-6,11-dioxo-3,4,6,11-tetrahydro-2(1H)-naphthacenylidene]ethyl acetate | C28H28O8 | 详情 | 详情 | |
(XVIII) | 50739 | (2S,4R)-2-[2-(acetoxy)acetyl]-4-(tert-butoxy)-2,12-dihydroxy-6,11-dioxo-1,2,3,4,6,11-hexahydro-5-naphthacenyl acetate | C28H28O10 | 详情 | 详情 |