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Dichloromethane → 2-amino-5-(4-{[tert-butyl(dimethyl)silyl]oxy}cyclohex-1-en-1-yl)-N,N-dimethylbenzamide

HRID 511402
ノート
印刷プレビュー

反応式

HRID 511402 の反応式
[NH2:1][C:2]1[CH:12]=[CH:11][C:10](B2OC(C)(C)C(C)(C)O2)=[CH:9][C:3]=1[C:4]([N:6]([CH3:8])[CH3:7])=[O:5].[C:22]([Si:26]([CH3:43])([CH3:42])[O:27][CH:28]1[CH2:33][CH2:32][C:31](OS(C(F)(F)F)(=O)=O)=[CH:30][CH2:29]1)([CH3:25])([CH3:24])[CH3:23].ClCCl.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[NH2:1][C:2]1[CH:12]=[CH:11][C:10]([C:31]2[CH2:32][CH2:33][CH:28]([O:27][Si:26]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:42])[CH3:43])[CH2:29][CH:30]=2)=[CH:9][C:3]=1[C:4]([N:6]([CH3:7])[CH3:8])=[O:5]
参加物実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 534150124-((tert-Butyldimethylsilyl)oxy)cyclohex-1-en-1-yl trifluoromethanesulfonateHCID 574162382-amino-N,N-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide2 回

生成物 1

HCID 672614622-amino-5-(4-{[tert-butyl(dimethyl)silyl]oxy}cyclohex-1-en-1-yl)-N,N-dimethylbenzamide

試薬・触媒・溶媒 3

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

実験手順

A solution of 2-amino-N,N-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide (Compound 173D: 0.500 g, 1.72 mmol) and trifluoro-methanesulfonic acid 4-(tert-butyl-dimethyl-silanyloxy)-cyclohex-1-enyl ester (WO 2005092863, 0.745 g, 2.07 mmol) in 1,4-dioxane (4 mL) and H2O (1 mL) was charged with [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (0.063 g, 0.086 mmol) and potassium carbonate (0.71 g, 5.2 mmol) in a microwave vial. The reaction mixture was evacuated and purged with nitrogen (3×) and irradiated in the microwave for 30 min at 100° C. The reaction mixture was partitioned between EtOAc and water and separated. The aqueous was extracted with EtOAc (3×) and the combined organic fractions were washed with brine, dried over sodium sulfate, filtered, and concentrated. The compound was purified on an Isco Combiflash eluting with 50 to 100% EtOAc in heptane to afford the title compound. 1H NMR (400 MHz, DMSO-d6) δ 7.17 (dd, J=2.27, 8.59 Hz, 1H), 7.00 (d, J=2.27 Hz, 1H), 6.64 (d, J=8.59 Hz, 1H), 5.83 (d, J=2.02 Hz, 1H), 5.16 (s, 2H), 3.89-3.98 (m, 1H), 2.91 (br. s., 6H), 2.32-2.44 (m, 2H), 2.00-2.09 (m, 1H), 1.85 (d, J=10.86 Hz, 1H), 1.55-1.67 (m, 1H), 0.87 (s, 12H), 0.06 (d, J=2.27 Hz, 6H); MS (ES+): m/z: 375.2372 [MH+]. HPLC: tR=1.96 min (UPLC TOF MS: polar—3 min).

後処理

  1. customThe reaction mixture was evacuated
  2. custompurged with nitrogen (3×)
  3. customirradiated in the microwave for 30 min at 100° C
  4. customThe reaction mixture was partitioned between EtOAc and water
  5. customseparated
  6. extractionThe aqueous was extracted with EtOAc (3×)
  7. washthe combined organic fractions were washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe compound was purified on an Isco Combiflash
  12. washeluting with 50 to 100% EtOAc in heptane

出典と根拠

ORDレコード
ord-ab2e414ba65849048f17fffe991a490b
出典データセット
uspto-grants-2015_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09096624B2

反応ノート

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