Diisopropylethylamine → 3-(1,2,3,9b-Tetraaza-cyclopenta[a]naphthalen-7-ylsulfanyl)-propionic acid 2-ethyl-hexyl ester

HRID 2075715Notes

Reaction equation

HRID 2075715 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]1[N:12]=[N:13][N:14]=[C:7]1[CH:6]=[CH:5]2.[CH2:15]([CH:17]([CH2:25][CH2:26][CH2:27][CH3:28])[CH2:18][O:19][C:20](=[O:24])[CH2:21][CH2:22][SH:23])[CH3:16].CCN(C(C)C)C(C)C.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>O1CCOCC1.CCOC(C)=O.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:15]([CH:17]([CH2:25][CH2:26][CH2:27][CH3:28])[CH2:18][O:19][C:20](=[O:24])[CH2:21][CH2:22][S:23][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]1[N:12]=[N:13][N:14]=[C:7]1[CH:6]=[CH:5]2)[CH3:16]

Participants

9

Reactant 4

HCID 81531DiisopropylethylamineHCID 926402-Ethylhexyl 3-mercaptopropionateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 582578107-Bromo-1,2,3,9b-tetraaza-cyclopenta[a]naphthalene

Product 1

HCID 670906863-(1,2,3,9b-Tetraaza-cyclopenta[a]naphthalen-7-ylsulfanyl)-propionic acid 2-ethyl-hexyl ester

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
130 °C

Procedure

9d (233 mg, 0.88 mmol) and 3-mercaptopropionic acid 2-ethylhexyl ester (86 mg, 0.38 mmol) were dissolved in 1,4-dioxane (10 mL) and degassed with N2 for 10 minutes. iPr2NEt (0.33 mL, 1.80 mmol) was added, followed by Pd2dba3 (20 mg, 0.02 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (23 mg, 0.04 mmol). The reaction was sealed and heated overnight at 130° C., and then cooled to room temperature and diluted with EtOAc and water. The organic layer was washed with water and brine, dried over MgSO4, filtered, and concentrated. The residue was purified by silica gel chromatography (0-20% MeOH in EtOAc) to give the desired product, 9e.

Workup

  1. customdegassed with N2 for 10 minutes
  2. customThe reaction was sealed
  3. temperaturecooled to room temperature
  4. washThe organic layer was washed with water and brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by silica gel chromatography (0-20% MeOH in EtOAc)

Sources & evidence

ORD record
ord-0deed5c071a04957aefbad4aa97c74eb
Source dataset
uspto-grants-2011_04
Patent number
US07919621B2

Reaction notes

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