Ammonium Chloride → (3aR,5S,6aR)-2,2-dimethyl-5-[(2R)-oxiran-2-yl]-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole

HRID 60696ノート

反応式

HRID 60696 の反応式
CC1C=CC(S(O[CH2:12][C@H:13]([C@H:15]2[O:24][C@@H:18]3[O:19][C:20]([CH3:23])([CH3:22])[O:21][C@@H:17]3[CH2:16]2)[OH:14])(=O)=O)=CC=1.C[Si]([N-][Si](C)(C)C)(C)C.[K+].[NH4+].[Cl-]>C1COCC1>[CH3:22][C:20]1([CH3:23])[O:19][C@H:18]2[O:24][C@H:15]([C@H:13]3[CH2:12][O:14]3)[CH2:16][C@H:17]2[O:21]1

参加物

5

反応物 3

HCID 25517Ammonium ChlorideHCID 3251421Potassium bis(trimethylsilyl)amideHCID 15473566[(2R)-2-[(3aR,5S,6aR)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-hydroxy-ethyl] 4-methylbenzenesulfonate2 回

生成物 1

HCID 10910249(3aR,5S,6aR)-2,2-dimethyl-5-[(2R)-oxiran-2-yl]-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole収率 77.7%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-70 °C

実験手順

To a solution of [(2R)-2-[(3aR,5S,6aR)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-hydroxy-ethyl] 4-methylbenzenesulfonate (compound 6a, 100 g, 280 mmol) in anhydrous THF (1500 mL) cooled at −70° C. was added potassium bis(trimethylsilyl)amide (340 mL, 340 mmol, 1 M in THF) under N2 atmosphere. After being stirred at −70° C. for 1 hour, the reaction mixture was poured into saturated NH4Cl solution. The organic layer was separated and the aqueous phase was extracted with EtOAc. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 1:3 EtOAc in petroleum ether) to afford 40.5 g of (3aR,5S,6aR)-2,2-dimethyl-5-[(2R)-oxiran-2-yl]-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole (compound 6b) as a slight yellow oil.

後処理

  1. customThe organic layer was separated
  2. extractionthe aqueous phase was extracted with EtOAc
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by column chromatography on silica gel (eluting with 1:3 EtOAc in petroleum ether)

出典と根拠

ORDレコード
ord-0bac61f13d1a47729c73cbeecbe5f4b7
出典データセット
uspto-grants-2016_09
特許番号
US09441008B2

反応ノート

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