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【结 构 式】 
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【分子编号】34439 【品名】5,8,8-trimethyl-2H,8H-pyrano[2,3-f]chromen-2-one 【CA登记号】 |
【 分 子 式 】C15H14O3 【 分 子 量 】242.27436 【元素组成】C 74.36% H 5.82% O 19.81% |
合成路线1
该中间体在本合成路线中的序号：(VIII)Vilsmeier formylation of orcinol (I) by means of POCl3 and DMF afforded 2,4-dihydroxy-6-methylbenzaldehyde (II). Coumarin (V) was then prepared by Wittig condensation of (II) with carbethoxymethylene triphenylphosphorane (III) followed by intramolecular cyclization in refluxing xylene. Alkylation of (V) with 3-chloro-3-methyl-1-butyne (VI) in the presence of K2CO3 and KI produced the corresponding alpha,alpha-dimethylpropargyl ether (VII), and subsequent thermal cyclization in refluxing N,N-diethylaniline gave rise to the tricyclic system (VIII). Osmium-catalyzed asymmetric dihydroxylation of (VIII) in the presence of the enantioselective ligand hydroquinone 2,5-diphenyl-4,6-pyrimidinediyl diether [(DHQ)2-PYR] produced the required (R,R)-(+)-cis-diol (IX). This was finally acylated with (S)-(-)-camphanic chloride (X) in the presence of pyridine to produce the target dicamphanoyl ester.
| 【1】 Takeuchi, Y.; Xie, L.; Lee, K.-H.; Cosentino, L.M.; Anti-AIDS agents. 37.(1) synthesis and structure-activity relationships of (3'R,4'R)-(+)-cis-khellactone derivatives as novel potent anti-HIV agents. J Med Chem 1999, 42, 14, 2662. |
| 【2】 Xie, L.; Takeuchi, Y.; Cosentino, L.M.; Lee, K.-H.; Anti-AIDS agent 33. Synthesis and anti-HIV activity of mono-methyl substituted 3',4'-di-O-(-)-camphanoyl-(+)-cis-khellactone (DCK) analogues. Bioorg Med Chem Lett 1998, 8, 16, 2151. |
| 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) | 27257 | 5-Methyl-1,3-benzenediol; Orcinol | 505-15-4 | C7H8O2 | 详情 | 详情 |
| (II) | 34435 | 2,4-dihydroxy-6-methylbenzaldehyde | C8H8O3 | 详情 | 详情 | |
| (III) | 14182 | ethyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate; (Carbethoxymethylene)triphenylphosphorane | 1099-45-2 | C22H21O2P | 详情 | 详情 |
| (IV) | 34436 | ethyl (E)-3-(2,4-dihydroxy-6-methylphenyl)-2-propenoate | C12H14O4 | 详情 | 详情 | |
| (V) | 34437 | 7-hydroxy-5-methyl-2H-chromen-2-one | C10H8O3 | 详情 | 详情 | |
| (VI) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (VII) | 34438 | 7-[(1,1-dimethyl-2-propynyl)oxy]-5-methyl-2H-chromen-2-one | C15H14O3 | 详情 | 详情 | |
| (VIII) | 34439 | 5,8,8-trimethyl-2H,8H-pyrano[2,3-f]chromen-2-one | C15H14O3 | 详情 | 详情 | |
| (IX) | 34440 | (9R,10R)-9,10-dihydroxy-5,8,8-trimethyl-9,10-dihydro-2H,8H-pyrano[2,3-f]chromen-2-one | C15H16O5 | 详情 | 详情 | |
| (X) | 16583 | (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl chloride; (-)-Camphanic chloride | 39637-74-6 | C10H13ClO3 | 详情 | 详情 |