Chloroiodomethane → chloromethyl 5-(N-CBz-L-valyloxy)-2,2-dimethylvalerate

HRID 1170600ノート

反応式

HRID 1170600 の反応式
[C:1]([NH:11][C@H:12]([C:16]([O:18][CH2:19][CH2:20][CH2:21][C:22]([CH3:27])([CH3:26])[C:23]([OH:25])=[O:24])=[O:17])[CH:13]([CH3:15])[CH3:14])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].[OH-].C([N+](CCCC)(CCCC)CCCC)CCC.[Cl:46][CH2:47]I>O1CCOCC1>[C:1]([NH:11][C@H:12]([C:16]([O:18][CH2:19][CH2:20][CH2:21][C:22]([CH3:27])([CH3:26])[C:23]([O:25][CH2:47][Cl:46])=[O:24])=[O:17])[CH:13]([CH3:14])[CH3:15])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2]

参加物

5

反応物 3

HCID 11644ChloroiodomethaneHCID 2723671Tetrabutylammonium HydroxideHCID 233875555-(N-CBz-L-valyloxy)-2,2-dimethylvaleric acid

生成物 1

HCID 23387570chloromethyl 5-(N-CBz-L-valyloxy)-2,2-dimethylvalerate収率 59.6%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

To a solution of 5-(N-CBz-L-valyloxy)-2,2-dimethylvaleric acid (5.88 g, 15.5 mmol) in dioxane (100 mL), was added dropwise a 40% aqueous solution of tetrabutylammonium hydroxide (10.1 g). After stirring for 5 min, the solution was evaporated to dryness through co-evaporation with dioxane and toluene. The residue was dissolved in dichloromethane (100 mL) and then chloroiodomethane (11.3 mL, 155 mmol) was added and the solution was stirred for 6 h at room temperature. The solution was concentrated under reduced pressure and the residue was shaken with hexane/ethyl acetate (1:1 v/v, 200 mL). The yellow crystalline solid was filtered off and the filtrate was washed with aqueous solution of sodium thiosulfate (0.1 M) and the filtered through anhydrous sodium sulfate and evaporated to dryness. The residue was column chromatographed (silica gel, 1-4% MeOH in CH2Cl2), to give 3.95 g of chloromethyl 5-(N-CBz-L-valyloxy)-2,2-dimethylvalerate.

後処理

  1. customthe solution was evaporated to dryness through co-evaporation with dioxane and toluene
  2. dissolutionThe residue was dissolved in dichloromethane (100 mL)
  3. stirringthe solution was stirred for 6 h at room temperature
  4. concentrationThe solution was concentrated under reduced pressure
  5. stirringthe residue was shaken with hexane/ethyl acetate (1:1 v/v, 200 mL)
  6. filtrationThe yellow crystalline solid was filtered off
  7. washthe filtrate was washed with aqueous solution of sodium thiosulfate (0.1 M)
  8. filtrationthe filtered through anhydrous sodium sulfate
  9. customevaporated to dryness
  10. customchromatographed (silica gel, 1-4% MeOH in CH2Cl2)

出典と根拠

ORDレコード
ord-5185500350104b369cf9f6206ef47e4c
出典データセット
uspto-grants-2010_11
特許番号
US07825238B2

反応ノート

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