Water → ((2S,4R)-4-(tert-butyldimethylsilyloxy)-6-oxotetrahydro-2H-pyran-2-yl)methyl acetate

HRID 2387919ノート

反応式

HRID 2387919 の反応式
[Si:1]([O:8][C@@H:9]1[CH2:14][C@@H:13]([CH2:15]I)[O:12][C:11](=[O:17])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CC[O:20][C:21]([CH3:23])=[O:22].O>CC(O)=O.CC([O-])=O.[Ag+]>[C:21]([O:22][CH2:15][C@@H:13]1[CH2:14][C@@H:9]([O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[CH2:10][C:11](=[O:17])[O:12]1)(=[O:20])[CH3:23]

参加物

6

反応物 3

HCID 962WaterHCID 8857Ethyl AcetateHCID 10937529(4R,6S)-4-(tert-butyldimethylsilyloxy)-6-(iodomethyl)-tetrahydropyran-2-one

生成物 1

HCID 16113281((2S,4R)-4-(tert-butyldimethylsilyloxy)-6-oxotetrahydro-2H-pyran-2-yl)methyl acetate収率 92.6%

試薬・触媒・溶媒 2

HCID 11246Silver acetate触媒HCID 176Acetic Acid溶媒

実験手順

To the solution of (4R,6S)-4-(tert-butyldimethylsilyloxy)-6-(iodomethyl)-tetrahydropyran-2-one (6a) (40.00 g, 108.0 mmol) in AcOH (660 mL) is added AgOAc (20.03 g, 118.8 mmol). The resultant mixture is then heated at 125° C. for 6 hours. The reaction mixture is filtered through diatomite filter medium (Celite®). The obtained filtrate is evaporated to afford the residue. To this residue EtOAc (500 mL) and water (600 mL) are added. The organic layer is separated and the aqueous layer is washed again with EtOAc (5×150 mL). The combined organic layers are washed with water (4×300 mL), brine (5×300 mL) and dried over anhydrous MgSO4, filtered and concentrated under the reduced pressure to afford 30.28 g (92.6%) of ((2S,4R)-4-(tert-butyldimethylsilyloxy)-6-oxo-tetrahydro-2H-pyran-2-yl)methyl acetate (7) as yellow oil (HPLC purity 98%). 1H NMR (300 MHz, CDCl3): δ 4.93 (m, 1H), 4.37 (m, 1H), 4.30 (dd, J=12 Hz, J=3 Hz, 1H), 4.21 (dd, J=12 Hz, J=5 Hz, 1H), 2.62 (d, J=4 Hz, 2H), 2.11 (s, 3H), 1.84−1.80 (m, 2H), 0.89 (s, 9H), 0.09, 0.09 (2s, 6H). 13C NMR (75 MHz, CDCl3): δ 170.4, 169.1, 73.3, 65.5, 63.0, 38.9, 32.2, 20.5, 17.7, −5.1, −5.2.

後処理

  1. filtrationThe reaction mixture is filtered through diatomite
  2. filtrationfilter medium (Celite®)
  3. customThe obtained filtrate is evaporated
  4. customto afford the residue
  5. customThe organic layer is separated
  6. washthe aqueous layer is washed again with EtOAc (5×150 mL)
  7. washThe combined organic layers are washed with water (4×300 mL), brine (5×300 mL)
  8. dry with materialdried over anhydrous MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated under the reduced pressure

出典と根拠

ORDレコード
ord-c1ff5c642b5f4a9296446f60fefba515
出典データセット
uspto-grants-2012_09
特許番号
US08269001B2

反応ノート

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