cis-4-(t-Butyldimethylsilyloxymethyl)-2-(diethyloxyphosphinoyl)-1,3-dithiolane → cis 2-(Diethyloxyphosphinoyl)-4-hydroxymethyl-1,3-dithiolane

HRID 481717ノート

反応式

HRID 481717 の反応式
[Si]([O:8][CH2:9][C@H:10]1[CH2:14][S:13][C@@H:12]([P:15]([O:20][CH2:21][CH3:22])([O:17][CH2:18][CH3:19])=[O:16])[S:11]1)(C(C)(C)C)(C)C>CO.C(Cl)(=O)C.[Cl-].[NH4+]>[CH2:18]([O:17][P:15]([O:20][CH2:21][CH3:22])([C@H:12]1[S:11][C@@H:10]([CH2:9][OH:8])[CH2:14][S:13]1)=[O:16])[CH3:19]

参加物

5

反応物 1

HCID 131720784cis-4-(t-Butyldimethylsilyloxymethyl)-2-(diethyloxyphosphinoyl)-1,3-dithiolane

生成物 1

HCID 86752990cis 2-(Diethyloxyphosphinoyl)-4-hydroxymethyl-1,3-dithiolane収率 77.6%

試薬・触媒・溶媒 3

HCID 6367Acetyl chloride触媒HCID 25517Ammonium Chloride触媒HCID 887Methanol溶媒

反応条件

温度
0 °C

実験手順

To a solution of cis-4-(t-butyldimethylsilyloxymethyl)-2-(diethyloxyphosphinoyl)-1,3-dithiolane (example 49) (3.70 g, 9.56 mmol) in anhydrous methanol (50 mL) was added acetyl chloride (6 drops) at 0° C. The solution was stirred at 0° C. for 30 min and then at room temperature for 4.5 hrs. A saturated solution of ammonium chloride (3 drops) was added and the solution was stirred for 15 min followed by evaporation of solvents. The crude material was purified by flash chromatography with a mixture of dichloromethane and methanol (95:5) to give the compound (2.02 g) in 77% yield. 1H NMR (300 MHz, CDCl3) δ: 1.34 (t, 6H, J=7.0 Hz, CH3), 3.30 (dd, 1H, J=5.5 Hz, 12.0 Hz, H-5a), 3.42 (dd, 1H, J=6.0 Hz, 12.1 Hz, H-5b), 3.80 (m, 2H, CH2OH and 1H, OH), 4.05 (m, 1H, H-4) , 4.19 (m, 4H, CH2) , 4.35 (d, 1H, 2JHP =4.1 Hz, H-2).

後処理

  1. waitat room temperature for 4.5 hrs
  2. stirringthe solution was stirred for 15 min
  3. customfollowed by evaporation of solvents
  4. customThe crude material was purified by flash chromatography with a mixture of dichloromethane and methanol (95:5)

出典と根拠

ORDレコード
ord-091340f044474edead9ae049ac6c895c
出典データセット
uspto-grants-1998_08
特許番号
US05789394

反応ノート

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