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【结 构 式】

【分子编号】36698

【品名】methyl (4S,5R,6R)-4-isopropenyl-2,2,5-trimethyl-6-vinyl-1,3-dioxane-5-carboxylate

【CA登记号】

【 分 子 式 】C14H22O4

【 分 子 量 】254.32628

【元素组成】C 66.12% H 8.72% O 25.16%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(VIII)

Boron-catalyzed condensation of propionyl oxazolidinone (I) with acrolein (II) stereoselectively provided the aldol product (III), and further methanolysis afforded beta-hydroxy ester (IV). A second aldol condensation of (IV) with methacrolein (V) furnished a difficultly separable mixture of diols (VI). Conversion of (VI) to the corresponding acetonides by treatment with 2-methoxypropene (VII) allowed chromatographical separation of the required major isomer (VIII). Hydrolysis of the acetonide, followed by ring-closing metathesis of diene (XI) in the presence of Grubbs catalyst gave rise to cyclopentene (XII). Selective silylation of the less hindered allylic hydroxyl of (XII) with tert-butyldimethylsilyl chloride yielding (XIII) and subsequent oxidation of the remaining alcohol group with MnO2 then provided ketone (XIV). Conjugate addition of lithium di-n-butylcuprate to the unsaturated ketone, followed by phenylselenylation of the intermediate enolate with PhSeBr yielded alpha-selenyl ketone (XV). Oxidative elimination of the phenylselenyl group gave a (1:1) mixture of the required unsaturated ketone (XVII) and its exomethylene isomer (XVI). Isomerization of (XVI) to the desired endo isomer (XVII) was carried out by treatment with RhCl3.

1 Sunazuka, T.; et al.; Total synthesis of (+)-madindoline A and (-)-madindoline B, potent, selective inhibitors of interleukin 6. Determination of the relative and absolute configurations. J Am Chem Soc 2000, 122, 9, 2122.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(VIa) 36695 methyl (2R,3R)-3-hydroxy-2-[(1R)-1-hydroxy-2-propenyl]-2,4-dimethyl-4-pentenoate C11H18O4 详情 详情
(VIb) 36696 methyl (2S,3R)-3-hydroxy-2-[(1R)-1-hydroxy-2-propenyl]-2,4-dimethyl-4-pentenoate C11H18O4 详情 详情
(VIc),(XI) 36697 methyl (2S,3S)-3-hydroxy-2-[(1R)-1-hydroxy-2-propenyl]-2,4-dimethyl-4-pentenoate C11H18O4 详情 详情
(I) 11535 (4S)-4-Isopropyl-3-propionyl-1,3-oxazolidin-2-one 77877-19-1 C9H15NO3 详情 详情
(II) 17668 acrylaldehyde; Acrolein 107-02-8 C3H4O 详情 详情
(III) 36693 (4S)-3-[(2S,3R)-3-hydroxy-2-methyl-4-pentenoyl]-4-isopropyl-1,3-oxazolidin-2-one C12H19NO4 详情 详情
(IV) 36694 methyl (2S,3R)-3-hydroxy-2-methyl-4-pentenoate C7H12O3 详情 详情
(V) 11387 2-Methylacrylaldehyde; Methacrylaldehyde 78-85-3 C4H6O 详情 详情
(VII) 17354 isopropenyl methyl ether; 2-methoxy-1-propene 116-11-0 C4H8O 详情 详情
(VIII) 36698 methyl (4S,5R,6R)-4-isopropenyl-2,2,5-trimethyl-6-vinyl-1,3-dioxane-5-carboxylate C14H22O4 详情 详情
(IX) 36699 methyl (4R,5R,6R)-4-isopropenyl-2,2,5-trimethyl-6-vinyl-1,3-dioxane-5-carboxylate C14H22O4 详情 详情
(X) 36700 methyl (4R,5S,6R)-4-isopropenyl-2,2,5-trimethyl-6-vinyl-1,3-dioxane-5-carboxylate C14H22O4 详情 详情
(XII) 36701 methyl (1S,2S,5R)-2,5-dihydroxy-1,3-dimethyl-3-cyclopentene-1-carboxylate C9H14O4 详情 详情
(XIII) 36702 methyl (1R,2S,5R)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-hydroxy-1,3-dimethyl-3-cyclopentene-1-carboxylate C15H28O4Si 详情 详情
(XIV) 36703 methyl (1S,5R)-5-[[tert-butyl(dimethyl)silyl]oxy]-1,3-dimethyl-2-oxo-3-cyclopentene-1-carboxylate C15H26O4Si 详情 详情
(XV) 36704 methyl (1S,5R)-4-butyl-5-[[tert-butyl(dimethyl)silyl]oxy]-1,3-dimethyl-2-oxo-3-(phenylselanyl)cyclopentanecarboxylate C25H40O4SeSi 详情 详情
(XVI) 36705 methyl (1S,2R)-3-butyl-2-[[tert-butyl(dimethyl)silyl]oxy]-1-methyl-4-methylene-5-oxocyclopentanecarboxylate C19H34O4Si 详情 详情
(XVII) 36706 methyl (1S,2R)-3-butyl-2-[[tert-butyl(dimethyl)silyl]oxy]-1,4-dimethyl-5-oxo-3-cyclopentene-1-carboxylate C19H34O4Si 详情 详情
Extended Information