Tetramethyltin → 1,6-anhydro-3,4-dideoxy-3-methyl-beta-D-glycero-hex-3-enopyranos-2-ulose

HRID 1769236Notes

Reaction equation

C[Sn](C)(C)C.[CH3:6]N1CCCC1=O.I[C:14]1[C:15](=[O:22])[C@@H:16]2[O:21][CH2:20][C@H:18]([CH:19]=1)[O:17]2.C1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cu]I.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.C(OCC)(=O)C>[CH3:6][C:14]1[C:15](=[O:22])[C@@H:16]2[O:21][CH2:20][C@H:18]([CH:19]=1)[O:17]2

Participants

Conditions

Temperature: 80 °C

Procedure

5.3 g of tetramethyltin was added to 20 ml of a dry N-methylpyrrolidinone solution containing a mixture comprising 5 g of 1,6-anhydro-3,4-dideoxy-3-iodo-β-D-glycero-hex-3-enopyranos-2-ulose, 0.4 g of copper(I) iodide, 0.6 g of triphenylarsine and 0.4 g of dichlorobis(benzonitrile)palladium(II) under an inert atmosphere of nitrogen gas. The mixture was stirred at 80° C. for 4 hours. Then, 200 ml of ethyl acetate was added thereto, and the mixture was washed three times with 100 ml of a 10% potassium fluoride aqueous solution. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained syrup product was purified by silica gel column chromatography (ethyl acetate: hexane=1:3) and then distilled under reduced pressure to obtain 1.61 g of the desired product (Intermediate No. 2) as a colorless transparent liquid. The NMR analytical data of this product are as follows.

Workup

washthe mixture was washed three times with 100 ml of a 10% potassium fluoride aqueous solution
dry with materialThe organic layer was dried over anhydrous sodium sulfate
distillationthe solvent was distilled off under reduced pressure
customThe obtained syrup product was purified by silica gel column chromatography (ethyl acetate: hexane=1:3)
distillationdistilled under reduced pressure

Sources & evidence

ORD record: ord-c715a54ebc0342aeb4d04ff8f7b30de9
Source dataset: uspto-grants-1995_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05380834

Reaction notes

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