Tetrahydrofuran → Lithium Hexamethyldisilazide

HRID 1735833Notes

Reaction equation

HRID 1735833 reaction equation
O1CCCC1.[CH3:6][Si:7]([CH3:14])([CH3:13])[NH:8][Si:9]([CH3:12])([CH3:11])[CH3:10].C([Li:19])CCC>CCCCCC>[CH3:6][Si:7]([CH3:14])([CH3:13])[N-:8][Si:9]([CH3:12])([CH3:11])[CH3:10].[Li+:19]

Participants

5

Reactant 3

HCID 8028Tetrahydrofuran2×HCID 13838HexamethyldisilazaneHCID 178418339Butyllithium

Product 1

HCID 2733832Lithium Hexamethyldisilazide

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

To a tetrahydrofuran (hereinafter referred to simply as THF) (90 ml) solution of hexamethyldisilazane (6.84 ml), 19.1 ml of n-butyl lithium (a 1.56 M hexane solution) was added at -78° C., and the mixture was stirred for 30 minutes to obtain a lithium hexamethyldisilazide solution. To this solution, a THF (20 ml) solution of 10 g of (1S,5R,6R,7R)-2-oxa-7-(2-tetrahydropyranyloxy)-6-(t-butyldimethylsiloxy)methyl-bicyclo[3.3.0]octan-3-one (Compound 1) was dropwise added at -78° C., and the mixture was stirred for 60 minutes. Then, a THF (40 ml) solution of 9.37 g of N-fluorobenzenesulfonimide was added thereto at -78° C. The mixture was stirred at -78° C. for 60 minutes, then stirred at room temperature for 30 minutes. Then, it was poured into a saturated sodium hydrogen carbonate aqueous solution, and the mixture was extracted with ethyl acetate. The extract was purified by silica gel column chromatography (ethyl acetate:hexane=1:8 to 1:4) to obtain 9.46 g of the above-identified compound. 1H-NMR (CDCl3) δ (ppm): 0.05 (m, 6H), 0.88 (m, 9H), 1.4-1.8 (m, 6H), 2.0-3.1 (m, 4H), 3.4-5.3 (m, 8H).

Workup

  1. additionwas added at -78° C.

Sources & evidence

ORD record
ord-d0a075e8a8d94c929d33715b15f49312
Source dataset
uspto-grants-1996_07
Patent number
US05538995

Reaction notes

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