Cesium carbonate → tert-butyl 2-(N-methylformamido)-7-(2-(2-(2-(tosyloxy)ethoxy)ethoxy)ethoxy)-9H-carbazole-9-carboxylate

HRID 1425575Notes

Reaction equation

HRID 1425575 reaction equation
[OH:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([N:15]([CH3:18])[CH:16]=[O:17])=[CH:9][CH:10]=3)[N:5]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C:4]=2[CH:3]=1.[CH3:26][C:27]1[CH:32]=[CH:31][C:30]([S:33]([O:36][CH2:37][CH2:38][O:39][CH2:40][CH2:41][O:42][CH2:43][CH2:44]F)(=[O:35])=[O:34])=[CH:29][CH:28]=1.C([O-])([O-])=O.[Cs+].[Cs+]>CN1C(=O)CCC1.CCOC(C)=O>[CH3:18][N:15]([C:8]1[CH:9]=[CH:10][C:11]2[C:12]3[C:4](=[CH:3][C:2]([O:1][CH2:44][CH2:43][O:42][CH2:41][CH2:40][O:39][CH2:38][CH2:37][O:36][S:33]([C:30]4[CH:29]=[CH:28][C:27]([CH3:26])=[CH:32][CH:31]=4)(=[O:35])=[O:34])=[CH:14][CH:13]=3)[N:5]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C:6]=2[CH:7]=1)[CH:16]=[O:17]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 58225214tert-butyl 2-hydroxy-7-(N-methylformamido)-9H-carbazole-9-carboxylateHCID 595523472-[2-(2-Fluoroethoxy)ethoxy]ethyl 4-methylbenzene-1-sulfonate

Product 1

HCID 86651373tert-butyl 2-(N-methylformamido)-7-(2-(2-(2-(tosyloxy)ethoxy)ethoxy)ethoxy)-9H-carbazole-9-carboxylateYield 63%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To tert-butyl 2-hydroxy-7-(N-methylformamido)-9H-carbazole-9-carboxylate (65 mg, 0.19 mmol) and 2-(2-(2-fluoroethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (174 mg, 0.38 mmol) in 0.5 mL NMP was added Cs2CO3 (68 mg, 0.21 mmol). The mixture was stirred at rt for 15 h under Ar atmosphere and diluted with EtOAc (80 mL). It was washed with water (3×50 mL), and dried over MgSO4. Solvent was removed under reduced pressure and the crude product was purified with silica chromatography (hexane/EtOAc) to afford tert-butyl 2-(N-methylformamido)-7-(2-(2-(2-(tosyloxy)ethoxy)ethoxy)ethoxy)-9H-carbazole-9-carboxylate (AD-CB-004Pb-WZ01191) as a clear oil (75 mg, 63%). 1H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 8.14 (s, 1H), 7.89 (s, 1H), 7.87 (d, J=8.0 Hz, 1H), 7.83 (d, J=8.8 Hz, 1H), 7.79 (m, 2H), 7.32 (d, J=8.4 Hz, 2H), 7.15 (dd, J=8.4, 2.0 Hz, 1H), 7.00 (dd, J=8.8, 2.4 Hz, 1H), 4.23 (m, 1H), 3.89 (m, 2H), 3.88 (m, 2H), 3.73-3.68 (m, 4H), 3.66-3.63 (m, 2H), 3.41 (s, 3H), 2.42 (s, 3H), 1.76 (s, 9H); MS (ESI) m/z 527 (M+H+).

Workup

  1. washIt was washed with water (3×50 mL)
  2. dry with materialdried over MgSO4
  3. customSolvent was removed under reduced pressure
  4. customthe crude product was purified with silica chromatography (hexane/EtOAc)

Sources & evidence

ORD record
ord-18d03a583c724e1293f5b865d5562fe9
Source dataset
uspto-grants-2015_01
Patent number
US08932557B2

Reaction notes

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