1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 66838847, compound

HRID 1808693Notes

Reaction equation

HRID 1808693 reaction equation
Br[C:2]1[N:3]=[C:4]2[CH:10]=[CH:9][N:8]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[C:5]2=[N:6][CH:7]=1.[CH2:19]([N:22]1[CH2:27][CH2:26][S:25](=[O:29])(=[O:28])[CH2:24][CH2:23]1)[C:20]#[CH:21].[CH2:30]1CCN2C(=NCCC2)CC1>CC(N(C)C)=O.[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:24]([S:25]([CH2:26][CH2:27][N:22]([CH3:30])[C:19]1[N:3]2[C:2]([CH:7]=[N:6][C:5]3[N:8]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[CH:9]=[CH:10][C:4]=32)=[CH:21][CH:20]=1)(=[O:29])=[O:28])[CH3:23]

Participants

7

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 27772654-(Prop-2-yn-1-yl)-1lambda~6~,4-thiazinane-1,1-dioneHCID 575165972-bromo-5-((2-(trimethylsilyl)ethoxy)methyl)-5H-pyrrolo[2,3-b]pyrazine

Product 1

HCID 66838847HCID 66838847, compoundYield 59%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
80 °C

Procedure

A flask was charged with 2-bromo-5-(2-trimethylsilanyl-ethoxymethyl)-5H-pyrrolo[2,3-b]pyrazine (295 mg, 0.9 mmol), 4-propargyl-thiomorpholine-1,1-dioxide (commercial, 156 mg, 0.9 mmol), copper iodide (17 mg, 0.09 mmol), dichlorobis-(triphenylphosphine)palladium (II) (13 mg, 0.018 mmol) and DBU (0.4 mL, 2.7 mmol) in dry dimethyl acetamide (3 mL). The mixture was vacuum degassed and heated to 80° C. under argon. After 1.5 hours the material was warmed to 120° C. and stirred for 12 hours. The mixture was cooled to ambient and quenched via the addition of water (45 ml) and ethyl acetate (45 ml). The material was shaken in a reparatory funnel, and the ethyl acetate phase was collected. The aqueous phases were back extracted with ethyl acetate (2×40 ml), the organics combined, dried (MgSO4), filtered and stripped. The remainder was purified by preparative TLC using 45% ethyl acetate in hexanes as eluant to provide 232 mg of (2-ethanesulfonyl-ethyl)-methyl-[3-(2-trimethylsilanyl-ethoxymethyl)-3H-3,4,8a-triaza-as-indacen-8-yl]-amine as a dark brown oil. MS (M+H)+=421.

Workup

  1. customdegassed
  2. temperatureAfter 1.5 hours the material was warmed to 120° C.
  3. temperatureThe mixture was cooled to ambient and
  4. customquenched via the addition of water (45 ml) and ethyl acetate (45 ml)
  5. stirringThe material was shaken in a reparatory funnel
  6. customthe ethyl acetate phase was collected
  7. extractionThe aqueous phases were back extracted with ethyl acetate (2×40 ml)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. customThe remainder was purified by preparative TLC

Sources & evidence

ORD record
ord-810e7ab0de2645c49c50daac0e95750e
Source dataset
uspto-grants-2013_01
Patent number
US08361962B2

Reaction notes

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