Diethyl Ether → (3aS,4S,6S,7aR)-3a,5,5-Trimethyl-2-(2-methylpropyl)hexahydro-2H-4,6-methano-1,3,2-benzodioxaborole

HRID 1037735ノート

反応式

HRID 1037735 の反応式
[CH2:1]([Mg]Br)[CH:2]([CH3:4])[CH3:3].C(OCC)C.CC(O[B:16]1[O:20][C@@H:19]2[CH2:21][C@@H:22]3[CH2:25][C@H:24]([C@:18]2([CH3:28])[O:17]1)[C:23]3([CH3:27])[CH3:26])C.[Na+].[Cl-]>O1CCCC1.S(=O)(=O)(O)O.C(OC(C)C)(C)C>[CH3:3][CH:2]([CH3:4])[CH2:1][B:16]1[O:20][C@@H:19]2[CH2:21][C@@H:22]3[CH2:25][C@H:24]([C@:18]2([CH3:28])[O:17]1)[C:23]3([CH3:27])[CH3:26]

参加物

8

反応物 4

HCID 3283Diethyl EtherHCID 5234Sodium ChlorideHCID 66741716(3AS,4S,6S,7aR)-2-isopropoxy-3a,5,5-trimethylhexahydro-4,6-methanobenzo[d][1,3,2]dioxaboroleHCID 178418816HCID 178418816、化合物

生成物 1

HCID 12842239(3aS,4S,6S,7aR)-3a,5,5-Trimethyl-2-(2-methylpropyl)hexahydro-2H-4,6-methano-1,3,2-benzodioxaborole収率 62%

試薬・触媒・溶媒 3

HCID 1118Sulfuric Acid溶媒HCID 7914Diisopropyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

A 2M solution of isobutyl magnesium bromide in diethyl ether (131.5 ml, 0.263 mol) was added dropwise, in 1 hour, to a solution of 2-(1-methylethoxy)-(3aS,4S,6S,7aR)-hexahydro-3a,5,5-trimethyl-4,6-methano-1,3,2-benzodioxaborole obtained in Step 1 (62.6 g, 0.263 mol), in anhydrous tetrahydrofuran (330 ml) while stirring at −78° C., under nitrogen. The mixture was then allowed to warm to room temperature, then transferred in a mixture of 2N sulfuric acid (150 ml) and diisopropyl ether (250 ml). After stirring for 10 minutes, a saturated solution of NaCl was added (100 ml) and the layers were separated. The organic phase was washed with brine (100 ml), dried over sodium sulfate and concentrated. The residue was purified by column chromatography (silica gel) eluting with 5% diethyl ether in hexane. The product was obtained as a clear oil (38.45 g, 62% yield).

後処理

  1. temperatureto warm to room temperature
  2. stirringAfter stirring for 10 minutes
  3. customthe layers were separated
  4. washThe organic phase was washed with brine (100 ml)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by column chromatography (silica gel)
  8. washeluting with 5% diethyl ether in hexane

出典と根拠

ORDレコード
ord-c36fddb14b5e4c0ebf6975c9d2be2bca
出典データセット
uspto-grants-2013_10
特許番号
US08546608B2

反応ノート

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