Nitrogen → HCID 69895515, compound

HRID 2307068Notes

Reaction equation

HRID 2307068 reaction equation
Br[C:2]1[C:3]2[CH:4]3[CH2:22][CH2:21][N:20](C(OC(C)(C)C)=O)[CH2:19][CH2:18][CH:5]3[N:6](C(OC(C)(C)C)=O)[C:7]=2[CH:8]=[CH:9][CH:10]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[O:38]1[CH:42]=[CH:41][C:40](B(O)O)=[CH:39]1.N#N>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C=O)C>[O:38]1[CH:42]=[CH:41][C:40]([C:2]2[C:3]3[C@@H:4]4[CH2:22][CH2:21][NH:20][CH2:19][CH2:18][C@@H:5]4[NH:6][C:7]=3[CH:8]=[CH:9][CH:10]=2)=[CH:39]1

Participants

7

Reactant 4

HCID 947NitrogenHCID 62657Potassium Phosphate, TribasicHCID 2734358Furan-3-boronic acidHCID 69894587HCID 69894587, compound

Product 1

HCID 69895515HCID 69895515, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A 30-mL shaker vial was charged with di(tert-butyl) 10-bromo-1,2,4,5,5a,10b-hexahydroazepino[4,5-b]indole-3,6-dicarboxylate (0.10 g, 0.214 mmol), potassium phosphate (0.068 g, 0.32 mmol), furan-3-boronic acid (0.072 g, 0.642 mmol), and DMF (2 mL). The vial was purged with N2, and tetrakis(triphenylphosphine)-palladium (0.025 g, 0.02 mmol) was added and the mixture was agitated at 250 RPM with heating at 80° C. overnight. The mixture was filtered through Celite, washing with MeOH (3-5 mL), and sulfonic acid resin (DOWEX®50W-X2, washed and dried, 4.8 meq/g dry weight) was added (1 g). The vial was then purged with N2, capped and agitated at 250 RPM with heating at 65° C. for 72 h. The mixture was filtered through a scintered funnel and the resin was washed 1:1 methylene chloride/methanol and then consecutively washed with MeOH and THF to ensure that all excess reagent was removed from the resin (the methanol and THF washes are alternated to swell and then shrink the resin to help expel reagents from inside the resin). The resin was then washed with 4M ammonium hydroxide in methanol (4×2 ml) and THF (2×2 ml) into an accurately weight round-bottomed flask. The filtrate was concentrated to give 0.038 g (70%) of a pink oil: MS (EI) m/z 255 (MH+); HPLC rt=2.51 min (100%).

Workup

  1. additionwas added
  2. filtrationThe mixture was filtered through Celite
  3. washwashing with MeOH (3-5 mL), and sulfonic acid resin (DOWEX®50W-X2, washed and dried, 4.8 meq/g dry weight)
  4. additionwas added (1 g)
  5. customThe vial was then purged with N2
  6. customcapped
  7. stirringagitated at 250 RPM
  8. temperaturewith heating at 65° C. for 72 h
  9. filtrationThe mixture was filtered through a scintered funnel
  10. washthe resin was washed 1:1 methylene chloride/methanol
  11. washconsecutively washed with MeOH and THF
  12. customwas removed from the resin (the methanol and THF washes
  13. washThe resin was then washed with 4M ammonium hydroxide in methanol (4×2 ml) and THF (2×2 ml) into an accurately weight round-bottomed flask
  14. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-ec5a3e440df44b20a0095e0a74d2a6e8
Source dataset
uspto-grants-2004_12
Patent number
US06828314B2

Reaction notes

Loading…