Ethanol → HCID 117600802, compound

HRID 931616Notes

Reaction equation

HRID 931616 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C@:15]3([CH2:20][CH2:19][O:18][C:17]([NH2:21])=[N:16]3)[C:14]3[C:9](=[CH:10][CH:11]=[C:12](I)[CH:13]=3)[O:8][C:5]2=[N:6][CH:7]=1.[N-:23]=[N+:24]=[N-:25].[Na+].CCO.N[C@@H]1CCCC[C@H]1N>[Cu]I.O>[N:23]([C:12]1[CH:13]=[C:14]2[C@@:15]3([CH2:20][CH2:19][O:18][C:17]([NH2:21])=[N:16]3)[C:4]3[C:5](=[N:6][CH:7]=[C:2]([Br:1])[CH:3]=3)[O:8][C:9]2=[CH:10][CH:11]=1)=[N+:24]=[N-:25]

Participants

7

Reactant 4

HCID 702EthanolHCID 33557Sodium AzideHCID 438061,2-Diaminocyclohexane, trans-HCID 89473227HCID 89473227, compound2×

Product 1

HCID 117600802HCID 117600802, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolvent

Procedure

A microwave vial was charged with (S)-3-bromo-7-iodo-5′,6′-dihydrospiro[chromeno[2,3-b]pyridine-5,4′-[1,3]oxazin]-2′-amine (500 mg, 1.059 mmol, Intermediate 25), copper(I) iodide (20.17 mg, 0.106 mmol), (+)-sodium 1-ascorbate (10.49 mg, 0.053 mmol) and sodium azide (0.074 ml, 2.118 mmol). The vial was evacuated and backfilled with nitrogen. EtOH (2 ml), rac-trans-1,2-diaminocyclohexane (0.019 ml, 0.159 mmol) and water (0.9 ml) were added. The reaction mixture was heated overnight to 56° C. An additional portion of each reagent were added and the reaction was heated for additional 6 hours. The reaction mixture was partitioned between water and EtOAc. The organic phase was separated and dried over MgSO4. The solvent was removed under reduced pressure and the residue was purified by flash chromatography (silical gel, 20-100% EtOAc/hexanes) to afford (S)-7-azido-3-bromo-5′,6′-dihydrospiro[chromeno[2,3-b]pyridine-5,4′-[1,3]oxazin]-2′-amine as a yellow solid.

Workup

  1. customThe vial was evacuated
  2. temperatureThe reaction mixture was heated overnight to 56° C
  3. additionAn additional portion of each reagent were added
  4. temperaturethe reaction was heated for additional 6 hours
  5. customThe reaction mixture was partitioned between water and EtOAc
  6. customThe organic phase was separated
  7. dry with materialdried over MgSO4
  8. customThe solvent was removed under reduced pressure
  9. customthe residue was purified by flash chromatography (silical gel, 20-100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-86bfebb16d5d4f72aa51d8277b0ca78e
Source dataset
uspto-grants-2016_03
Patent number
US09296759B2

Reaction notes

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