Water → (4R,6S)-4-(tert-butyldimethylsilyloxy)-6-(dihydroxymethyl)-tetrahydropyran-2-one
Reaction equation
FC(F)(F)C([O-])=[O:4].FC1C=CC(C2C(C[P+](CCCC)(CCCC)CCCC)=C(C(C)C)N=C(N(C)S(C)(=O)=O)N=2)=CC=1.[Si:44]([O:51][C@H:52]1[CH2:57][C:56](=[O:58])[O:55][C@H:54]([CH:59]=[O:60])[CH2:53]1)([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45].O>C1(C)C=CC=CC=1>[Si:44]([O:51][C@@H:52]1[CH2:53][C@@H:54]([CH:59]([OH:4])[OH:60])[O:55][C:56](=[O:58])[CH2:57]1)([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Procedure
To a stirred suspension of ((4-(4-fluorophenyl)-6-isopropyl-2-(N-methylmethylsulfonamido)pyrimidin-5-yl)methyl)tributylphosphonium 2,2,2-trifluoro-acetate (50.4, 77 mmol) at room temperature in dry toluene (800 mL) sodium hexamethyldisilazane (NaHDMS) in toluene (130 mL of 0.6 M, 77 mmol) was added portionwise in 10 minutes. The reaction mixture was stirred for 60 min and treated at room temperature with a solution of (2S,4R)-4-(tert-butyldimethylsilyloxy)-6-oxo-tetrahydro-2H-pyran-2-carbaldehyde (20 g, 77 mmol) in 2.5 L of dry toluene obtained by dissolution of (4R,6S)-4-(tert-butyldimethylsilyloxy)-6-(dihydroxymethyl)-tetrahydropyran-2-one (21.4 g, 77 mmol) in toluene and removal of released water. After 24 hours of stirring at room temperature the solution was treated with saturated ammonium chloride solution or water. The aqueous phase was extracted with methyl t-butyl ether (2×2 L), and the combined organic layers dried and concentrated to give oily residue with 25-40% HPLC area of RSVLTBS.
Workup
- additionwas added portionwise in 10 minutes
Sources & evidence
- ORD record
- ord-c3a6d54c2fce44cc861382a713a52481
- Source dataset
- uspto-grants-2015_06
- Patent number
- US09067895B2
Reaction notes
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