Dimethyl Sulfoxide → (2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-[3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl]-tetrahydro-furan-2-carbaldehyde

HRID 25677

反応式

HRID 25677 の反応式
CS(C)=O.C(Cl)(=O)C(Cl)=O.[Si:11]([O:18][C@@H:19]1[C@H:23]([O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])[C@@H:22]([CH2:32][OH:33])[O:21][C@H:20]1[N:34]1[CH:39]=[CH:38][C:37](=[O:40])[N:36]([CH2:41][C:42]2[CH:47]=[CH:46][C:45]([O:48][CH3:49])=[CH:44][CH:43]=2)[C:35]1=[O:50])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C(N(CC)CC)C>C(Cl)Cl.C(OCC)(=O)C>[Si:25]([O:24][C@H:23]1[C@@H:19]([O:18][Si:11]([C:14]([CH3:16])([CH3:15])[CH3:17])([CH3:12])[CH3:13])[C@H:20]([N:34]2[CH:39]=[CH:38][C:37](=[O:40])[N:36]([CH2:41][C:42]3[CH:43]=[CH:44][C:45]([O:48][CH3:49])=[CH:46][CH:47]=3)[C:35]2=[O:50])[O:21][C@H:22]1[CH:32]=[O:33])([C:28]([CH3:29])([CH3:30])[CH3:31])([CH3:27])[CH3:26]

参加物

7

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 151026051-[(2R,3R,4R,5R)-3,4-bis{[tert-Butyl(dimethyl)silyl]oxy}-5-(hydroxymethyl)tetrahydro-2-furanyl]-3-(4-methoxybenzyl)-2,4(1H,3H)-pyrimidinedione

生成物 1

HCID 86587931(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-[3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl]-tetrahydro-furan-2-carbaldehyde収率 95.1%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

Following the literature procedure (Myers, A. G.; Gin, D. Y.; Rogers, D. H., J. Amer. Chem. Soc., 1994, 116, 4697-4718), anhydrous dimethyl sulfoxide (3.35 ml, 47.23 mmole) was added dropwise to a solution of oxalyl chloride (14.2 ml, 28.34 mmole, 2.0 M solution in methylene chloride, Aldrich) in anhydrous methylene chloride (50 ml) under argon at −78° C. The resulting mixture was stirred at −78° C. for 45 min, and was transferred via cannula to a cooled (−78° C.) solution of 1-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(hydroxymethyl)tetrahydro-2-furanyl]-3-(4-methoxybenzyl)-2,4(1H,3H)-pyrimidinedione (5.6 g, 9.45 mmole, obtained from Reference Example 2) in anhydrous methylene chloride (50 ml) under argon. The resulting mixture was stirred at −78° C. for 1 h, and triethylamine (9.9 ml, 70.8 mmole) was added all at once. The mixture was stirred at −78° C. for 1.5 h under argon, and diluted with ethyl acetate (500 ml). The organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated to dryness in vacuo. Toluene was added to the residue, and evaporated in vacuo. This procedure was repeated for two more times, to give 1-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-[3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl]-tetrahydro-furan-2-carbaldehyde as pale yellow solid (5.31 g, 95%). This material was used in its crude form in the following experiment. MS (ES): m/z 591.3 (M+H).

後処理

  1. stirringThe resulting mixture was stirred at −78° C. for 1 h
  2. stirringThe mixture was stirred at −78° C. for 1.5 h under argon
  3. washThe organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated to dryness in vacuo
  7. additionToluene was added to the residue
  8. customevaporated in vacuo

出典と根拠

ORDレコード
ord-803d2059deb34c5c9b6870ade81406d3
出典データセット
uspto-grants-2005_02
特許番号
US06858591B2

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