Dichloromethane → HCID 68006717, compound

HRID 1053904Notes

Reaction equation

HRID 1053904 reaction equation
Br[C:2]1[CH2:6][CH2:5][C:4](=[O:7])[C:3]=1[C:8]1[CH:13]=[CH:12][C:11]([C:14]([CH3:17])([CH3:16])[CH3:15])=[CH:10][CH:9]=1.CC1(C)C(C)(C)OB([C:26]2[CH:31]=[CH:30][C:29]([NH:32][C:33](=[O:39])[O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[CH:28][CH:27]=2)O1.ClCCl.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.O.C(OCC)(=O)C.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]>[C:14]([C:11]1[CH:12]=[CH:13][C:8]([C:3]2[C:4](=[O:7])[CH2:5][CH2:6][C:2]=2[C:26]2[CH:27]=[CH:28][C:29]([NH:32][C:33](=[O:39])[O:34][C:35]([CH3:37])([CH3:36])[CH3:38])=[CH:30][CH:31]=2)=[CH:9][CH:10]=1)([CH3:17])([CH3:16])[CH3:15]

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 2734617tert-butyl N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamateHCID 67975802HCID 67975802, compound

Product 1

HCID 68006717HCID 68006717, compoundYield 49.3%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of Example 7D (88 mg, 0.300 mmol), tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate (105 mg, 0.330 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (24.51 mg, 0.030 mmol) and K2CO3 (83 mg, 0.600 mmol) in 1,4-dioxane (2 mL) and water (0.5 mL) was stirred at 100° C. for 16 hours. The mixture was diluted with ethyl acetate (30 mL) and washed with brine (10 mL×4). The organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by preparative thin layer chromatography (eluted with petroleum ether/ethyl acetate=2:1, v/v) to afford the title compound (60 mg, 0.148 mmol, 49.3% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.28-7.36 (m, 6H), 7.14 (d, J=8.0 Hz, 2H), 6.52 (s, 1H), 3.00-3.03 (m, 2H), 2.66-2.69 (m, 2H), 1.51 (s, 9H), 1.32 (s, 9H); LC/MS (ESI) m/z 406 (M+H)+.

Workup

  1. washwashed with brine (10 mL×4)
  2. dry with materialThe organic layers were dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by preparative thin layer chromatography (
  6. washeluted with petroleum ether/ethyl acetate=2:1

Sources & evidence

ORD record
ord-dd79773edbc24908ad0083f83b0df9ec
Source dataset
uspto-grants-2016_07
Patent number
US09394279B2

Reaction notes

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