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HRID1969774

反应详情

EQUATION

反应方程式

HRID 1969774 的结构方程式

REACTANTS

反应物

2
结构：COc1ccc(P2(=S)SP(=S)(c3ccc(OC)cc3)S2)cc1
HCID87949

p-Anisyldithiophosphonic anhydride

C14H14O2P2S4

结构：Cc1ccc(S(=O)(=O)n2ccc3nc(CNC(=O)[C@H]4CN(C(=O)OC(C)(C)C)CC[C@H]4C)cnc32)cc1
HCID58557369

未命名化合物

PRODUCTS

生成物

1
结构：Cc1ccc(S(=O)(=O)n2ccc3c2ncc2cnc([C@H]4CN(C(=O)OC(C)(C)C)CC[C@H]4C)n23)cc1
HCID58557067

未命名化合物

收率 79.5%

AUXILIARIES

试剂、催化剂与溶剂

2
结构：O=C([O-])C(F)(F)F.O=C([O-])C(F)(F)F.[Hg+2]
催化剂HCID2723924

Mercury bis(trifluoroacetate)

C4F6HgO4

结构：C1COCCO1
溶剂HCID31275

1,4-Dioxane

C4H8O2

CONDITIONS

反应条件

温度
80 °C

PROCEDURE

实验过程

A mixture of (3R,4R)-tert-butyl-4-methyl-3-((5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)methyl-carbamoyl)-piperidine-1-carboxylate (53 g, 100 mmol) and Lawesson's reagent (22.4 g, 55.2 mmol) in 1,4-dioxane (500 mL) was heated at about 80° C. for about 1 h. The reaction was allowed to cool to ambient temperature and then was partitioned between EtOAc (1000 mL) and saturated aqueous NaHCO3 (700 mL). The organic layer was washed with additional saturated aqueous NaHCO3 (700 mL), dried over anhydrous Na2SO4, filtered then concd in vacuo. The resulting residue was dissolved in 1,4-dioxane (500 mL) then mercury (II) trifluoroacetate (54.0 g, 127 mmol) was added. The reaction was stirred at about 25° C. for about 1 h. The reaction was partitioned with saturated aqueous Na2S2O3 (500 mL)/water (500 mL) with DCM (1000 mL). The layers were filtered through Celite® and the Celite® pad was washed with DCM (500 mL). The combined layers were separated then the organic layer was washed with saturated aqueous NaHCO3 (800 mL). The organic layer was separated, dried over anhydrous Na2SO4, filtered, and then concd in vacuo. The resulting residue was purified on silica gel (330 g) using 0-40% EtOAc in DCM to give (3R,4R)-tert-butyl 4-methyl-3-(6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)piperidine-1-carboxylate (40.5 g, 79%) as a yellow foam: LC/MS (Table 1, Method b) Rt=2.62 min; MS m/z: 510 (M+H)+.

WORKUP

后处理

  1. temperatureto cool to ambient temperature
  2. customwas partitioned between EtOAc (1000 mL) and saturated aqueous NaHCO3 (700 mL)
  3. washThe organic layer was washed with additional saturated aqueous NaHCO3 (700 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. dissolutionThe resulting residue was dissolved in 1,4-dioxane (500 mL)
  7. customThe reaction was partitioned with saturated aqueous Na2S2O3 (500 mL)/water (500 mL) with DCM (1000 mL)
  8. filtrationThe layers were filtered through Celite®
  9. washthe Celite® pad was washed with DCM (500 mL)
  10. customThe combined layers were separated
  11. washthe organic layer was washed with saturated aqueous NaHCO3 (800 mL)
  12. customThe organic layer was separated
  13. dry with materialdried over anhydrous Na2SO4
  14. filtrationfiltered
  15. customThe resulting residue was purified on silica gel (330 g)