Cesium carbonate → HCID 178429687, compound

HRID 469913Notes

Reaction equation

HRID 469913 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@:9]1([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[C@H:14]([CH2:15][S:16][C:17]2[CH:22]=[CH:21][C:20]([F:23])=[C:19]([CH3:24])[CH:18]=2)[C@H:13](OS(C)(=O)=O)[C@@H:12]2[C@H:10]1[C@H:11]2[C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].[NH:50]1[CH:54]=[N:53][C:52]([SH:55])=[N:51]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>CN(C)C=O>[C:1]([O:5][C:6]([NH:8][C@@:9]1([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[C@H:14]([CH2:15][S:16][C:17]2[CH:22]=[CH:21][C:20]([F:23])=[C:19]([CH3:24])[CH:18]=2)[C@@H:13]([S:55][C:52]2[N:53]=[CH:54][NH:50][N:51]=2)[C@@H:12]2[C@H:10]1[C@H:11]2[C:30]([O:32][C:33]([CH3:35])([CH3:34])[CH3:36])=[O:31])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 5049666Sodium triacetoxyborohydrideHCID 86665755Di-tert-butyl (1S,2R,3S,4R,5R,6R)-2-(tert-butoxycarbonylamino)-3-[(4-fluoro-3-methyl-phenyl)sulfanylmethyl]-4-methylsulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylateHCID 178527894HCID 178527894, compound

Product 1

HCID 178429687HCID 178429687, compoundYield 16.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

Di-tert-butyl (1S,2R,3S,4R,5R,6R)-2-(tert-butoxycarbonylamino)-3-[(4-fluoro-3-methyl-phenyl)sulfanylmethyl]-4-methylsulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylate (5.3 g, 8.21 mmol) is dissolved in dimethylformamide (100 mL). To this mixture is added cesium carbonate (5.40 g, 16.41 mmol), 1H-1,2,4-triazole-3-thiol (3.42 g, 32.83 mmol), and sodium triacetoxyborohydride (906 mg, 4.10 mmol). The mixture is stirred at 40° C. for 72 hours. The reaction is cooled and quenched with water and aqueous NH4Cl. The mixture is transferred to a separatory funnel and extracted with diethyl ether, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give a residue. The residue is purified by flash chromatography (0 to 50% ethyl acetate/hexanes) to give the title compound (0.88 g, 1.35 mmol, 16.5% yield). MS (m/z): 651 (M+H).

Workup

  1. temperatureThe reaction is cooled
  2. customquenched with water and aqueous NH4Cl
  3. customThe mixture is transferred to a separatory funnel
  4. extractionextracted with diethyl ether
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto give a residue
  9. customThe residue is purified by flash chromatography (0 to 50% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-364ab32e95154037bf5b8d9a596bcca9
Source dataset
uspto-grants-2014_01
Patent number
US08629169B2

Reaction notes

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