Bromide ion → HCID 44451358, compound

HRID 638820Notes

Reaction equation

HRID 638820 reaction equation
[Br-].Br[C:3]1[CH:8]=[CH:7][C:6]([C@H:9]2[CH2:26][C@@:24]3([CH3:25])[C@@H:20]([CH2:21][C@@H:22]([CH3:32])[C@@H:23]3[C:27]([CH:29]3[CH2:31][CH2:30]3)=[O:28])[C@H:19]3[C:10]2=[C:11]2[C:16]([CH2:17][CH2:18]3)=[CH:15][C:14](=[O:33])[CH2:13][CH2:12]2)=[CH:5][CH:4]=1.[NH4+:34].[Cl-]>C1COCC1.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.[Pd](Cl)Cl.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2]>[CH:29]1([C:27]([C@H:23]2[C@H:22]([CH3:32])[CH2:21][C@H:20]3[C@H:19]4[C:10]([C@@H:9]([C:6]5[CH:5]=[CH:4][C:3]([C:7]6[CH:8]=[CH:3][CH:4]=[CH:5][N:34]=6)=[CH:8][CH:7]=5)[CH2:26][C@:24]23[CH3:25])=[C:11]2[C:16](=[CH:15][C:14](=[O:33])[CH2:13][CH2:12]2)[CH2:17][CH2:18]4)=[O:28])[CH2:30][CH2:31]1

Participants

7

Reactant 3

HCID 259Bromide ionHCID 25517Ammonium ChlorideHCID 68576237HCID 68576237, compound

Product 1

HCID 44451358HCID 44451358, compoundYield 40%

Reagents, catalysts & solvents 3

HCID 131728027Ferrocene palladium dichlorideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

(PPh3)2PdCl2 (4 mg, 0.006 mmol), ferrocene palladium dichloride (6 mg, 0.009 mmol) and 2-pyridylzine bromide (2 mL, 1.0 mmol) were added to a solution of (11β,16α,17β)-11-(4-bromophenyl)-17-cyclopropylcarbonyl-16-methylestra-4,9-dien-3-one (200 mg, 0.41 mmol) in THF (4 mL) under a nitrogen atmosphere. The reaction mixture was stirred for 5 hours at 60° C. and then cooled to room temperature. A saturated aqueous NH4Cl solution was added and the mixture was extracted three times with dichloromethane. The combined organic layers were dried through a phase separate filter and evaporated to dryness. Purification by HPLC followed by lyophilisation gave (11β,16α,17β)-17-cyclopropylcarbonyl-16-methyl-11-[4-(2-pyridinyl)phenyl]estra-4,9-dien-3-one (80 mg, 0.16 mmol, 40% yield). 1H NMR (400 MHz, CDCl3): δ 0.33 (s, 3H), 0.80-2.87 (m, 24H), 4.46 (d, J=7 Hz, 1H), 5.80 (s, 1H), 7.20-7.23 (m, 1H), 7.25-7.29 (m, 2H), 7.68-7.77 (m, 2H), 7.89-7.92 (m, 2H), 8.67 (dt, J=5 and 1 Hz, 1H).

Workup

  1. temperaturecooled to room temperature
  2. extractionthe mixture was extracted three times with dichloromethane
  3. customThe combined organic layers were dried through a phase
  4. customseparate
  5. filtrationfilter
  6. customevaporated to dryness
  7. customPurification by HPLC

Sources & evidence

ORD record
ord-cb2201264d884d09b4fb168309d50bb6
Source dataset
uspto-grants-2010_04
Patent number
US07691836B2

Reaction notes

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