Sodium Carbonate → {4-[4-(tert-Butyl-dimethyl-silanyloxy)-cyclohex-1-enyl]-phenyl}-carbamic acid benzyl ester

HRID 1027405노트

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HRID 1027405 반응식
[CH2:1]([O:8][C:9]([NH:11][C:12]1[CH:17]=[CH:16][C:15](B(O)O)=[CH:14][CH:13]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li+].[Cl-].C([O-])([O-])=O.[Na+].[Na+].[C:29]([Si:33]([CH3:50])([CH3:49])[O:34][CH:35]1[CH2:40][CH2:39][C:38](OS(C(F)(F)F)(=O)=O)=[CH:37][CH2:36]1)([CH3:32])([CH3:31])[CH3:30]>C1(C)C=CC=CC=1.CCOC(C)=O.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCO>[CH2:1]([O:8][C:9](=[O:10])[NH:11][C:12]1[CH:17]=[CH:16][C:15]([C:38]2[CH2:39][CH2:40][CH:35]([O:34][Si:33]([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:49])[CH3:50])[CH2:36][CH:37]=2)=[CH:14][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

참가 물질

10

반응물 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 27733224-(Benzyloxycarbonylamino)phenylboronic Acid (contains varying amounts of Anhydride)HCID 534150124-((tert-Butyldimethylsilyl)oxy)cyclohex-1-en-1-yl trifluoromethanesulfonate

생성물 1

HCID 67478826{4-[4-(tert-Butyl-dimethyl-silanyloxy)-cyclohex-1-enyl]-phenyl}-carbamic acid benzyl ester수율 98%

시약·촉매·용매 5

HCID 178418397HCID 178418397, 화합물촉매HCID 702Ethanol용매HCID 962Water용매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

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온도
100 °C

실험 절차

4-Benzyloxycarbonylamino-benzene boronic acid (1.42 g, 5.25 mmol, 1.5 equiv.) and LiCl (420 mg, 10.5 mmol, 3 equiv.) was placed in a 25 mL round bottom flask. To this was added Na2CO3 (2M) (7 mL) and EtOH (7 mL) to form a nice suspension. To this was transferred a solution of trifluoromethanesulfonic acid 4-(tert-butyl-dimethyl-silanyloxy)-cyclohex-1-enyl ester (1.26 g, 3.5 mmol, 1 equiv.) in toluene (18 mL). This suspension was subjected to a vacuum/nitrogen exchange three times. Pd(PPh3)4 (CAS 14221-01-3) (203 mg, 0.05 mmol, 7.5 mol %) was then added. The brown mixture was heated in an oil bath at 100° C. (external) for 50 min when the suspension became dark. At which time the TLC showed that the reaction was complete. The reaction was diluted with EtOAc (20 mL) and water (10 mL). The two layers were separated, and the aqueous layer was extracted with EtOAc (10 mL×2). The combined EtOAc extracts were washed with sodium bicarbonate (5 mL), brine (5 mL), dried (anhydrous potassium carbonate), filtered, and concentrated in vacuo to obtain a crude product. This was purified on a silica gel column eluted with 30% EtOAc in heptane to afford 1.5 g (98% yield) of the title compound as a crystalline white solid.

후처리

  1. customto form a nice suspension
  2. customThe two layers were separated
  3. extractionthe aqueous layer was extracted with EtOAc (10 mL×2)
  4. washThe combined EtOAc extracts were washed with sodium bicarbonate (5 mL), brine (5 mL)
  5. dry with materialdried (anhydrous potassium carbonate)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto obtain a crude product
  9. customThis was purified on a silica gel column
  10. washeluted with 30% EtOAc in heptane

출처 및 근거

ORD 기록
ord-36ff28766c3c4b42b72d2b8017d3a161
출처 데이터셋
uspto-grants-2014_05
특허 번호
US08735385B2

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