Triethylamine → HCID 22396616, compound

HRID 1370475Notes

Reaction equation

HRID 1370475 reaction equation
[C:1]([N:9]1[CH2:22][CH2:21][C:20]2[C:19]3[C:18](Br)=[CH:17][CH:16]=[CH:15][C:14]=3[NH:13][C:12]=2[CH2:11][CH2:10]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCN(CC)CC.[CH3:31][C:32]1([CH3:39])[C:36]([CH3:38])([CH3:37])[O:35][BH:34][O:33]1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCOCC1>[C:1]([N:9]1[CH2:22][CH2:21][C:20]2[C:19]3[C:18]([B:34]4[O:35][C:36]([CH3:38])([CH3:37])[C:32]([CH3:39])([CH3:31])[O:33]4)=[CH:17][CH:16]=[CH:15][C:14]=3[NH:13][C:12]=2[CH2:11][CH2:10]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 223966193-Benzoyl-10-bromo-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole

Product 1

HCID 22396616HCID 22396616, compoundYield 69.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

3-Benzoyl-10-bromo-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole (15.0 g, 40.6 mmol) was combined with dioxane (350 mL) at rt under N2. Et3N (34.0 mL, 24.7 g, 244 mmol) and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.4 mL, 9.37 g, 73.2 mmol) were added to the mixture by syringe. trans-Dichlorobis(triphenylphosphine)palladium(II) (1.44 g, 2.04 mmol) was added and Ar was bubbled through the reaction mixture for 20 min. The reaction mixture was refluxed under N2 for 18 h. The cooled reaction mixture was concentrated and the residue was combined with EtOAc (500 mL) and H2O (200 mL). The layers were separated and the aqueous layer was extracted with EtOAc (2×100 mL). The combined organic extracts were dried over MgSO4, filtered and concentrated. The crude product (22.9 g) was recrystallized from CH3OH (50 mL) to give 3-benzoyl-10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole (11.7 g) in 69% yield. MS (ESI+) for C25H29BN2O3 m/z 417.2 (M+H)+.

Workup

  1. customAr was bubbled through the reaction mixture for 20 min
  2. temperatureThe reaction mixture was refluxed under N2 for 18 h
  3. customThe cooled reaction mixture
  4. concentrationwas concentrated
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc (2×100 mL)
  7. dry with materialThe combined organic extracts were dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude product (22.9 g) was recrystallized from CH3OH (50 mL)

Sources & evidence

ORD record
ord-0db24931b7864ac1a857f20366baeb74
Source dataset
uspto-grants-2003_06
Patent number
US06583135B2

Reaction notes

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