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

HRID 589319노트

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HRID 589319 반응식
[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]

참가 물질

8

반응물 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, 화합물

생성물 1

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

시약·촉매·용매 3

HCID 1118Sulfuric Acid용매HCID 7914Diisopropyl Ether용매HCID 8028Tetrahydrofuran용매

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온도
-78 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-ae8c83e3d4ec402aa05b6acd585a4749
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09233115B2

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