Water → (4R,6S)-4-(tert-butyldimethylsilyloxy)-6-(dihydroxymethyl)-tetrahydropyran-2-one

HRID 2176863ノート

反応式

HRID 2176863 の反応式
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]

参加物

5

反応物 3

HCID 962WaterHCID 16113282(2S,4R)-4-(tert-butyldimethylsilyloxy)-6-oxo-tetrahydro-2H-pyran-2-carbaldehydeHCID 49783151((4-(4-fluorophenyl)-6-isopropyl-2-(N-methylmethylsulfonamido)pyrimidin-5-yl)methyl)tributylphosphonium 2,2,2-trifluoro-acetate

生成物 1

HCID 44128178(4R,6S)-4-(tert-butyldimethylsilyloxy)-6-(dihydroxymethyl)-tetrahydropyran-2-one収率 100%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒4 回

実験手順

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.

後処理

  1. additionwas added portionwise in 10 minutes

出典と根拠

ORDレコード
ord-c3a6d54c2fce44cc861382a713a52481
出典データセット
uspto-grants-2015_06
特許番号
US09067895B2

反応ノート

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