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Dimethyl Sulfoxide → (S,4E)-3-(tert-Butyldimethylsilyloxy)-4-methyl-5-(2-methyl-thiazol-4-yl)-pent-4-enal

HRID 1700960
ノート
印刷プレビュー

反応式

HRID 1700960 の反応式
CS(C)=O.C(Cl)(=O)C(Cl)=O.[Si:11]([O:18][C@H:19](/[C:23](/[CH3:31])=[CH:24]/[C:25]1[N:26]=[C:27]([CH3:30])[S:28][CH:29]=1)[CH2:20][CH2:21][OH:22])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C(N(CC)CC)C>ClCCl.O>[Si:11]([O:18][C@H:19](/[C:23](/[CH3:31])=[CH:24]/[C:25]1[N:26]=[C:27]([CH3:30])[S:28][CH:29]=1)[CH2:20][CH:21]=[O:22])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:12])[CH3:13]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10936330(-)-(3S,4E)-3-{[tert-Butyl(dimethyl)silyl]oxy}-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)pent-4-en-1-ol

生成物 1

HCID 11045612(S,4E)-3-(tert-Butyldimethylsilyloxy)-4-methyl-5-(2-methyl-thiazol-4-yl)-pent-4-enal収率 82.2%

試薬・触媒・溶媒 2

HCID 962Water溶媒
HCID 6344Dichloromethane溶媒3 回

反応条件

温度
-78 °C

実験手順

A solution of dimethyl sulfoxide (2,04 ml, 28.8 mmol, 2.4 equiv) in 6.0 ml of dichloromethane is added dropwise within 5 min to a stirred solution of oxalyl chloride (1.14 ml, 13.2 mmol, 1.1 equiv) in 30 ml of dichloromethane cooled to −78° C. The mixture is stirred for 10 min at −70° C. A solution of (S,4E)-3-(tert-butyldimethylsilyloxy)-1-hydroxy-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-ene 16 (3.93 g, 12.0 mmol) in 5 ml of dichloromethane is added dropwise within 5 min. The mixture is stirred for 30 min at −70° C. The reaction is quenched by dropwise addition of triethyl amine (8.4 ml, 60.0 mmol). The mixture is warmed to r.t. within 45 min. Water (30 ml) is added and the mixture is stirred for 10 min. The organic layer is seperated and the aqueous layer is extracted with dichloromethane (3×100 ml). The combined organic extracts are dried over magnesium sulfate and concentrated in vacuo. Purification of the residue by flash column chromatography (pentane/diethyl ether 5:2) affords (S,4E)-3-(tert-butyadimethylsilyloxy)-4-methyl-5-(2-methylthiazol-4-yl)-pent-4en-1-al 17 (3.21 g, 82%) as a pale yellow oil.

後処理

  1. stirringThe mixture is stirred for 30 min at −70° C
  2. temperatureThe mixture is warmed to r.t. within 45 min
  3. stirringthe mixture is stirred for 10 min
  4. customThe organic layer is seperated
  5. extractionthe aqueous layer is extracted with dichloromethane (3×100 ml)
  6. dry with materialThe combined organic extracts are dried over magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customPurification of the residue by flash column chromatography (pentane/diethyl ether 5:2)

出典と根拠

ORDレコード
ord-0b1aecd625f3441f91906c3800560430
出典データセット
uspto-grants-2002_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06350878B1

反応ノート

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