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

HRID 1947972
Notes
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Reaction equation

HRID 1947972 reaction equation
[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]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 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×

Product 1

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

Reagents, catalysts & solvents 3

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-d2499743154644aca4fdad13e5ce4617
Source dataset
uspto-grants-2013_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08399433B2

Reaction notes

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