Silane, tris(1-methylethyl)- → HCID 58843597, compound

HRID 501898Notes

Reaction equation

HRID 501898 reaction equation
C([SiH](C(C)C)C(C)C)(C)C.[CH2:11]([O:18][C@@H:19]1[C@@H:25]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@H:24]([O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[C@@H:23]([CH2:42][O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[O:22][C:20]1([C:51]1[CH:56]=[C:55]([CH3:57])[CH:54]=[CH:53][C:52]=1[O:58][CH2:59][C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)O)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=O)(O)[O-].[Na+]>>[CH2:11]([O:18][C@@H:19]1[C@@H:25]([O:26][CH2:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[C@H:24]([O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[C@@H:23]([CH2:42][O:43][CH2:44][C:45]2[CH:46]=[CH:47][CH:48]=[CH:49][CH:50]=2)[O:22][C@H:20]1[C:51]1[CH:56]=[C:55]([CH3:57])[CH:54]=[CH:53][C:52]=1[O:58][CH2:59][C:60]1[CH:61]=[CH:62][CH:63]=[CH:64][CH:65]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

4

Reactant 3

HCID 138754Silane, tris(1-methylethyl)-HCID 516892Sodium BicarbonateHCID 68457880HCID 68457880, compound

Product 1

HCID 58843597HCID 58843597, compound

Procedure

1.56 Moles of n-hexane solution of n-butyllithium (50 ml) were added dropwise to a solution of 1-(benzyloxy)-2-bromo-4-methylbenzene (20 g) in tetrahydrofuran (250 ml) at −78° C. in an argon atmosphere, and the mixture was stirred for one hour at the same temperature. To the reaction mixture was added dropwise a solution of 2,3,4,6-tetra-0-benzyl-D-(+)-glucono-1,5-lactone (35.0 g) in tetrahydrofuran (200 ml) at −78° C., and the resulting mixture was stirred for one hour at the same temperature. Aqueous solution of 1M hydrochloric acid (10 ml) was added to the mixture, and the temperature was raised to room temperature. Then, anhydrous magnesium sulfate (50 g) was added to the mixture, and the mixture was stirred for one hour at room temperature. After filtration, the filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography (n-hexane-ethyl acetate) to obtain 2,3,4,6-tetra-0-benzyl-1-C-[2-(benzyloxy)-5-methylphenyl]-D-glucopyranose (37 g). Triisopropylsilane (31 ml) and borontrifluoride diethylether complex (12.6 ml) were added to a solution of 2,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-methylphenyl]-D-glucopyranose in dicyclomethane-acetonitrile (1:3) (400 ml) under cooling with ice in an argon atmosphere, and the mixture was stirred for one hour at the same temperature. The reaction mixture was poured into saturated aqueous solution of sodium bicarbonate and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and filtrated, and then the solvent was evaporated from the filtrate under reduced pressure to give the residue. The residue was purified by silica gel column chromatography (n-hexane-ethyl acetate) to obtain (1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[2-(benzyloxy)-5-methylphenyl]-D-glucitol (16.9 g).

Workup

  1. temperatureunder cooling with ice in an argon atmosphere
  2. extractionextracted with chloroform
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. filtrationfiltrated
  5. customthe solvent was evaporated from the filtrate under reduced pressure
  6. customto give the residue
  7. customThe residue was purified by silica gel column chromatography (n-hexane-ethyl acetate)

Sources & evidence

ORD record
ord-7f7d870a7d164264a56ed135291c2cf1
Source dataset
uspto-grants-2010_08
Patent number
US07772407B2

Reaction notes

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