Cesium carbonate → HCID 90410529, compound

HRID 627069Notes

Reaction equation

HRID 627069 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:15][CH2:14][C:13]2[C:12]3[NH:16][CH:17]=[CH:18][C:11]=3[S:10][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2].I[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C([O-])([O-])=O.[Cs+].[Cs+].N[C@@H]1CCCC[C@H]1N>O1CCOCC1.C(Cl)Cl.[Cu]I>[CH2:1]([O:3][C:4]([N:6]1[CH2:15][CH2:14][C:13]2[C:12]3[N:16]([C:20]4[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=4)[CH:17]=[CH:18][C:11]=3[S:10][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 11575IodobenzeneHCID 438061,2-Diaminocyclohexane, trans-HCID 90410906HCID 90410906, compound

Product 1

HCID 90410529HCID 90410529, compoundYield 92.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of the product of Example 1, step (g) (0.056 g, 0.21 mmol) in dioxane (1.5 ml) under argon was added iodobenzene (0.026 ml, 0.23 mmol), Cs2CO3 (0.15 g, 0.45 mmol), CuI (0.002 g, 0.01 mmol), and (+)-trans-1,2-diaminocyclohexane (0.005 ml, 0.04 mmol). The reaction mixture was heated to 100° C. until LCMS indicated the reaction was complete (usually 16 hours). The reaction mixture was cooled to RT, diluted with DCM, and filtered through celite. The solvent was evaporated in vacuo and the residue purified by flash silica-gel chromatography (gradient elution: 0 to 50% EtOAc in hexanes) to give the sub-titled compound as a colorless oil (0.066 g). 1H NMR (CD3OD) δ 7.53-7.39 (m, 3H), 7.38-7.32 (m, 2H), 6.92 (d, J=3.0 Hz, 1H), 6.38 (d, J=3.0 Hz, 1H), 4.18-4.06 (m, 2H), 3.68-3.58 (m, 2H), 3.48-3.42 (m, 2H), 3.00-2.94 (m, 2H), 2.54-2.46 (m, 2H), 1.30-1.16 (m, 3H); MS: ESI (positive): 341 (M+H).

Workup

  1. customusually 16 hours
  2. temperatureThe reaction mixture was cooled to RT
  3. filtrationfiltered through celite
  4. customThe solvent was evaporated in vacuo
  5. customthe residue purified by flash silica-gel chromatography (gradient elution: 0 to 50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-f63dd5360481473c859319da0503c616
Source dataset
uspto-grants-2016_04
Patent number
US09309262B2

Reaction notes

Loading…