Water → HCID 57585828, compound

HRID 547660Notes

Reaction equation

HRID 547660 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[CH2:7][CH:6]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:5]2.O.[CH3:20][N:21](C)C=O>C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[C-]#N.[Zn+2].[C-]#N>[C:20]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[CH2:7][CH:6]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:5]2)#[N:21]

Participants

7

Reactant 3

HCID 962WaterHCID 6228DimethylformamideHCID 57585894322692-47-7

Product 1

HCID 57585828HCID 57585828, compoundYield 78%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 15826098Cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(diphenyl)phosphane;iron(2+)Catalyst

Conditions

Temperature
110 °C

Procedure

A flask containing 1,1-dimethylethyl (5-bromo-2,3-dihydro-1H-inden-2-yl)carbamate (3.0 g, 9.26 mmol) from the preceding step, diphenylphosphinoferrocene (645 mg, 1.16 mmol), Pd2 dba3 (532 mg, 0.58 mmol), zinc cyanide (1.50 g, 12.8 mmol) and water in 50 mL dimethylformamide was degassed four times under nitrogen and allowed to stir at 110° C. for 21 hours. Upon cooling the reaction was quenched with saturated NH4Cl and the organics were taken up in ethyl acetate. The organic layer was washed with water (3×), sat. NaCl and dried over MgSO4. The solvent was removed in vacuo and the residual orange-yellow oil was purified by silica gel column chromatography (15-40% ethyl acetate/hexanes) yielding 1.85 g (7.18 mmol, 78% yield) of the 1,1-dimethylethyl (5-cyano-2,3-dihydro-1H-inden-2-yl)carbamate as an off-white solid. 1H NMR (400 MHz, CDCl3) delta 7.47 (s, 1H), 7.45 (d, 1H, J=7.9 Hz), 7.28 (d, 1H, J=7.7 Hz), 4.69 (br.s), 1H), 4.47 (s(br), 1H), 3.33-3.25 (m, 2H), 2.86-2.80 (m, 2H), 2.79 (s, 9H) ppm. (M+1) 259.1, 2.46 min (LC/MS method A).

Workup

  1. customwas degassed four times under nitrogen
  2. temperatureUpon cooling the reaction
  3. customwas quenched with saturated NH4Cl
  4. washThe organic layer was washed with water (3×), sat. NaCl
  5. dry with materialdried over MgSO4
  6. customThe solvent was removed in vacuo
  7. customthe residual orange-yellow oil was purified by silica gel column chromatography (15-40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-4054291e337f4baba72c0123be33ba33
Source dataset
uspto-grants-2011_05
Patent number
US07939528B2

Reaction notes

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