Water → Bruceantin

HRID 1702965Notes

Reaction equation

HRID 1702965 reaction equation
[CH3:1][C@@H:2]1[C:28](=[O:29])[C:27]([O:30][C@@H]2O[C@H](CO)[C@@H](O)[C@H](O)[C@H]2O)=[CH:26][C@@:25]2([CH3:42])[C@H:3]1[CH2:4][C@H:5]1[O:14][C:12](=[O:13])[C@H:11]([O:15][C:16]([CH:18]=[C:19]([CH3:21])C)=[O:17])[C@@H:10]3[C@:6]41[C@@H:24]2[C@@H:23]([OH:43])[C@H:22]([OH:44])[C@@:9]3([C:45]([O:47][CH3:48])=[O:46])[O:8][CH2:7]4.[CH3:49][C:50](C(C)C)=[CH:51]C(Cl)=O.C(Cl)(Cl)Cl.CO.O.O>N1C=CC=CC=1.C(Cl)(Cl)Cl>[CH3:1][C:2]1[C@@H:3]2[CH2:4][C@H:5]3[O:14][C:12](=[O:13])[C@H:11]([O:15][C:16](/[CH:18]=[C:19](/[CH:50]([CH3:51])[CH3:49])\[CH3:21])=[O:17])[C@@H:10]4[C@@:6]53[CH2:7][O:8][C@:9]4([C:45]([O:47][CH3:48])=[O:46])[C@@H:22]([OH:44])[C@H:23]([OH:43])[C@@H:24]5[C@@:25]2([CH3:42])[CH2:26][C:27](=[O:30])[C:28]=1[OH:29]

Participants

7

Reactant 4

HCID 962WaterHCID 441789Methyl 2-(hexopyranosyloxy)-11,12-dihydroxy-15-[(3-methylbut-2-enoyl)oxy]-3,16-dioxo-13,20-epoxypicras-1-en-21-oate2×HCID 21866399Chloroform methanol waterHCID 541273923,4-Dimethyl-2-pentenoylchloride

Product 1

HCID 5281304BruceantinYield 58%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6212ChloroformSolvent

Procedure

A solution of 15-desenecioyl bruceoside-A (VI, 89.9 mg, 0.15 mmol) in dry pyridine (2 mL) was added dropwise to a solution of 3,4-dimethyl-2-pentenoyl chloride (IX, 330 mg, 2.25 mmol) in dry chloroform (2 mL). The mixture was stirred at room temperature for 20 hours until the thin layer chromatography (chloroform-methanol-water, 50:14:3) showed the disappearance of (VI), water was then added to decompose the unreacted acid chloride. The reaction product without further purification and isolation, was dissolved in dichloromethane (10 mL), and then borontrifluoride etherate (six drops) added. The reaction mixture was stirred at room temperature and examined by thin layer chromatography (chloroform-acetone, 1:1). After 4 days, the product was subjected to preparative thin layer chromatography (chloroform-acetone, 10:1) to yield pure bruceantin (V, 47.7 mg, 58% yield).

Workup

  1. additionwas then added
  2. customThe reaction product without further purification and isolation
  3. dissolutionwas dissolved in dichloromethane (10 mL)
  4. additionborontrifluoride etherate (six drops) added

Sources & evidence

ORD record
ord-d5f0d8745a5446959dfc8a1b78cb17fa
Source dataset
uspto-grants-1982_09
Patent number
US04350638

Reaction notes

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