【结 构 式】 |
【分子编号】56903 【品名】(8R,9R)-5-hydroxy-8,9-dimethyl-4-propyl-8,9-dihydro-2H,10H-pyrano[2,3-f]chromene-2,10-dione 【CA登记号】 |
【 分 子 式 】C17H18O5 【 分 子 量 】302.32692 【元素组成】C 67.54% H 6% O 26.46% |
合成路线1
该中间体在本合成路线中的序号:(IX)The cyclization of phloroglucinol (I) with 3-oxohexanoic acid methyl ester (II) by means of conc. sulfuric acid gives the benzopyranone (III), which is acylated with 2-methyl-2-butenoyl chloride (IV) and AlCl3 in dichloroethane to yield the 5-hydroxy-7-(2-methyl-2-butenoyloxy)-4-propylbenzopyran-2-one (V). This compound, without isolation, rearranges under the reaction conditions to afford 5,7-dihydroxy-8-(2-methyl-2-butenoyloxy)-4-propylbenzopyran-2-one (VI). The cyclization of (VI) with 3-methyl-2-butenal (VII) in refluxing pyridine provides the benzo-tripyran-2,12-dione derivative (VIII) -alternatively, conversion of (VI) into (VIII) can be performed by first cyclization of (VI) by means of TEA to furnish compound (IX), which is then subjected to cyclization with 3-methyl-2-butenal (VII)-. Finally, reduction of (VIII) with LiAlH(OBu)3 in THF provides the target calanolide A.
【1】 Terashima, S.; Koyakumaru, K. (Kuraray Co., Ltd.; Sagami Chemical Research Center); Processes for preparing calanolide A and intermediates thereof. JP 2002193971; WO 0251847 . |
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) | 11799 | 1,3,5-Benzenetriol; Fluoroglucinol | 108-73-6 | C6H6O3 | 详情 | 详情 |
(II) | 12516 | ethyl 3-oxohexanoate; ethyl butyrylacetate | 3249-68-1 | C8H14O3 | 详情 | 详情 |
(III) | 22405 | 5,7-dihydroxy-4-propyl-2H-chromen-2-one | C12H12O4 | 详情 | 详情 | |
(IV) | 45730 | Tigloyl chloride; (E)-2-methyl-2-butenoyl chloride | 35660-94-7 | C5H7ClO | 详情 | 详情 |
(V) | 56901 | 5-hydroxy-2-oxo-4-propyl-2H-chromen-7-yl (E)-2-methyl-2-butenoate | C17H18O5 | 详情 | 详情 | |
(VI) | 56902 | 5,7-dihydroxy-8-[(E)-2-methyl-2-butenoyl]-4-propyl-2H-chromen-2-one | C17H18O5 | 详情 | 详情 | |
(VII) | 19512 | (2S,3aR,7aS)octahydro-1H-indole-2-carboxylic acid | 145438-94-4 | C9H15NO2 | 详情 | 详情 |
(VIII) | 22410 | (10R,11R)-6,6,10,11-tetramethyl-4-propyl-10,11-dihydro-2H,6H,12H-dipyrano[2,3-f:2,3-h]chromene-2,12-dione | C22H24O5 | 详情 | 详情 | |
(IX) | 56903 | (8R,9R)-5-hydroxy-8,9-dimethyl-4-propyl-8,9-dihydro-2H,10H-pyrano[2,3-f]chromene-2,10-dione | C17H18O5 | 详情 | 详情 |