Cesium carbonate → HCID 86653490, compound

HRID 1505843Notes

Reaction equation

HRID 1505843 reaction equation
Br[C:2]1[CH:24]=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1.[C:25](=O)([O:27]C(C)(C)C)[NH2:26].C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4[C:52](=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)[C:51]([CH3:74])([CH3:73])C=3C=CC=2)C=CC=CC=1>O1CCOCC1.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]>[C:51]([C:2]1[C:24]([N:26]=[C:25]=[O:27])=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1)([CH3:52])([CH3:73])[CH3:74]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 58266568HCID 58266568, compound

Product 1

HCID 86653490HCID 86653490, compoundYield 813.6%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 3-bromo-9-(2-trimethylsilanylethoxymethyl)dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (1.53 g, 3.79 mmol), tert-butyl carbamate (888 mg, 7.58 mmol), and cesium carbonate (2.47 g, 7.58 mmol) were suspended in 1,4-dioxane (30 mL) degassed and purged with nitrogen three times. 4,5-bis(Diphenylphosphino)-9,9-dimethylxanthene (219 mg, 0.379 mmol) and tris(dibenzylideneacetone)dipalladium(0) (173 mg, 0.189 mmol) were added and the reaction mixture heated at 90° C. for 25 h. The cooled reaction mixture was pre-absorbed onto silica gel and purified by flash chromatography on silica (silica, 120 g column, Biotage, 10-60% EtOAc in heptane) to afford the title compound as a white-yellow solid (1.3 g, 80%). 1H NMR (400 MHz, DMSO-D6): 9.74 (s, 1H), 9.26 (s, 1H), 9.02 (s, 1H), 8.95 (s, 1H), 8.67 (d, J=2.4, 1H), 5.98 (s, 2H), 3.55 (t, J=7.9, 2H), 1.52 (s, 9H), 0.81 (t, J=7.9, 2H), −0.12-−0.23 (m, 9H).

Workup

  1. customdegassed
  2. custompurged with nitrogen three times
  3. customThe cooled reaction mixture
  4. customwas pre-absorbed onto silica gel
  5. custompurified by flash chromatography on silica (silica, 120 g column, Biotage, 10-60% EtOAc in heptane)

Sources & evidence

ORD record
ord-8052b4dcbecd4acba929ecbda052127e
Source dataset
uspto-grants-2015_12
Patent number
US09216980B2

Reaction notes

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