Cesium carbonate → HCID 86670472, compound

HRID 1911856Notes

Reaction equation

HRID 1911856 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].Br[C:8]1[N:13]=[C:12]([CH2:14][N:15]([CH3:52])[C:16]([C:18]2[CH:51]=[CH:50][C:21]([CH2:22][C@H:23]3[CH2:27][CH2:26][C@@H:25]([C@H:28]([O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[N:24]3[C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44])=[CH:20][CH:19]=2)=[O:17])[CH:11]=[CH:10][CH:9]=1.CC(CC(C)=O)=O.[OH-].[NH4+:61]>[Cu]I.CN(C=O)C>[NH2:61][C:8]1[N:13]=[C:12]([CH2:14][N:15]([CH3:52])[C:16]([C:18]2[CH:51]=[CH:50][C:21]([CH2:22][C@H:23]3[CH2:27][CH2:26][C@@H:25]([C@H:28]([O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[N:24]3[C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44])=[CH:20][CH:19]=2)=[O:17])[CH:11]=[CH:10][CH:9]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 14923Ammonium HydroxideHCID 31261AcetylacetoneHCID 86670471HCID 86670471, compound

Product 1

HCID 86670472HCID 86670472, compoundYield 105.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

In a round bottom flask was added CuI (0.54 mg, 2.8 μmol, 0.1 equivalents), Cs2CO3 (18.3 mg, 0.056 mmol, 2 equivalents), and tert-butyl (2R,5S)-2-(4-{[(6-bromopyridin-2-yl)methyl](methyl)carbamoyl}benzyl)-5-[(R)-{[tert-butyl(dimethyl)silyl]oxy}(phenyl)methyl]-pyrrolidine-1-carboxylate (20 mg, 0.028 mmol). The flask was evacuated and backfilled with nitrogen (3×) and then 2,4-pentadione (1.69 mg, 0.017 mmol, 0.6 equivalents), DMF (141 μL) and ammonium hydroxide (19.6 μL, 0.141 mmol, 5 equivalents) was added. The contents were transferred to a sealed tube under positive nitrogen pressure. The reaction was stirred and heated at 90° C. for 16 hours. The reaction was cooled and filtered over celite and washed with EtOAc. The EtOAc was washed with water and the aqueous layer was extracted with. EtOAc (3×). The organic extracts were then dried over Na2SO4, filtered, and concentrated in vacuo to afford the crude product (19 mg) that was taken directly onto the next step. LC-MS=646.3 (M+H)+.

Workup

  1. customThe flask was evacuated
  2. customThe contents were transferred to a sealed tube under positive nitrogen
  3. temperatureThe reaction was cooled
  4. filtrationfiltered over celite
  5. washwashed with EtOAc
  6. washThe EtOAc was washed with water
  7. extractionthe aqueous layer was extracted with
  8. dry with materialThe organic extracts were then dried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8374059adc744344bc3ca2442a68f371
Source dataset
uspto-grants-2013_12
Patent number
US08604038B2

Reaction notes

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