2,4-Bis(4-phenoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane → tert-butyl 4-(6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)bicyclo[2.2.2]octan-1-ylcarbamate

HRID 2204552Notes

Reaction equation

HRID 2204552 reaction equation
[S:1]([N:11]1[C:15]2=[N:16][CH:17]=[C:18]([CH2:20][NH:21][C:22]([C:24]34[CH2:31][CH2:30][C:27]([NH:32][C:33](=[O:39])[O:34][C:35]([CH3:38])([CH3:37])[CH3:36])([CH2:28][CH2:29]3)[CH2:26][CH2:25]4)=O)[N:19]=[C:14]2[CH:13]=[CH:12]1)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].O(C1C=CC(P2(=S)SP(=S)(C3C=CC(OC4C=CC=CC=4)=CC=3)S2)=CC=1)C1C=CC=CC=1>C1COCC1.CCOC(C)=O.C(O[Hg]OC(=O)C)(=O)C>[S:1]([N:11]1[C:15]2[N:16]=[CH:17][C:18]3[N:19]([C:22]([C:24]45[CH2:29][CH2:28][C:27]([NH:32][C:33](=[O:39])[O:34][C:35]([CH3:36])([CH3:38])[CH3:37])([CH2:30][CH2:31]4)[CH2:26][CH2:25]5)=[N:21][CH:20]=3)[C:14]=2[CH:13]=[CH:12]1)([C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[CH:9][CH:10]=1)(=[O:3])=[O:2]

Participants

6

Reactant 2

HCID 118134142,4-Bis(4-phenoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetaneHCID 58010034tert-butyl-4-((5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)methylcarbamoyl)bicyclo[2.2.2]octan-1-ylcarbamate

Product 1

HCID 58009897tert-butyl 4-(6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)bicyclo[2.2.2]octan-1-ylcarbamateYield 88.3%

Reagents, catalysts & solvents 3

HCID 16683746DiacetyloxymercuryCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of tert-butyl 4-((5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)methylcarbamoyl)-bicyclo[2.2.2]octan-1-ylcarbamate (0.205 g, 0.370 mmol) in THF (5 mL) was added 2,4-bis(4-phenoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (0.215 g, 0.407 mmol, TCI America). After about 15 h at ambient temperature, diacetoxymercury (0.295 g, 0.926 mmol) was added to the reaction mixture. After about 2 h, the reaction mixture was diluted with EtOAc (30 mL) and filtered through Celite®. The filtrate was concentrated under reduced pressure and the crude mixture was purified by chromatography on silica gel eluting with a gradient of 20-80% EtOAc in DCM to provide tert-butyl 4-(6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)bicyclo[2.2.2]octan-1-ylcarbamate as a tan solid (0.175 g, 84%). LC/MS (Table 2, Method a) Rt=2.84 min; MS m/z: 536 (M+H)+.

Workup

  1. waitAfter about 2 h
  2. filtrationfiltered through Celite®
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customthe crude mixture was purified by chromatography on silica gel eluting with a gradient of 20-80% EtOAc in DCM

Sources & evidence

ORD record
ord-abfd4156476e4c3d9bc899573a4239f8
Source dataset
uspto-grants-2016_06
Patent number
US09365579B2

Reaction notes

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