Dimethylformamide → tert-Butyl [7-cyano-1-(3,4-dichlorobenzyl)-1,2,3,4-tetrahydronaphthalen-2-yl]carbamate

HRID 2177079Notes

Reaction equation

HRID 2177079 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[CH2:13][CH2:12][CH:11]([NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH:10]([CH2:25][C:26]3[CH:31]=[CH:30][C:29]([Cl:32])=[C:28]([Cl:33])[CH:27]=3)[C:9]=2[CH:8]=1)(=O)=O.[CH3:36][N:37](C)C=O>ClCCl.C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2].[C-]#N.[Zn+2].[C-]#N>[C:21]([O:20][C:18](=[O:19])[NH:17][CH:11]1[CH2:12][CH2:13][C:14]2[C:9](=[CH:8][C:7]([C:36]#[N:37])=[CH:16][CH:15]=2)[CH:10]1[CH2:25][C:26]1[CH:31]=[CH:30][C:29]([Cl:32])=[C:28]([Cl:33])[CH:27]=1)([CH3:24])([CH3:23])[CH3:22]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 574672097-[(tert-Butoxycarbonyl)amino]-8-(3,4-dichlorobenzyl)-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate

Product 1

HCID 57467208tert-Butyl [7-cyano-1-(3,4-dichlorobenzyl)-1,2,3,4-tetrahydronaphthalen-2-yl]carbamate

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 15826098Cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(diphenyl)phosphane;iron(2+)CatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
90 °C

Procedure

Diphenylphosphinoferrocene (100 mg, 0.18 mmol) and dipalladium trisdibenzylideneacetone (41 mg, 0.045 mmol) were suspended under an atmosphere of argon in dry dimethylformamide (5 mL). After stirring at room temperature for 40 min 7-[(tert-butoxycarbonyl)amino]-8-(3,4-dichlorobenzyl)-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate (0.5 g, 0.902 mmol) was added and the reaction mixture was heated to 90° C. Over 30 min zinc cyanide (159 mg, 1.353 mmol) was added in small portions. After complete addition stirring was continued at 90° C. for 2 h. The reaction mixture was cooled to room temperature diluted with dichloromethane (50 mL), washed with saturated NaHCO3 (3×10 mL). The organic layer was dried (MgSO4) and concentrated in vacuo. The crude product was purified by flash chromatography (dichloromethane, silica gel). Yield: 97 mg (0.225 mmol, 25%).

Workup

  1. additionwas added
  2. additionAfter complete addition
  3. temperatureThe reaction mixture was cooled to room temperature
  4. washwashed with saturated NaHCO3 (3×10 mL)
  5. dry with materialThe organic layer was dried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by flash chromatography (dichloromethane, silica gel)

Sources & evidence

ORD record
ord-a28b724fc93f4508bd3342148400e3c8
Source dataset
uspto-grants-2015_06
Patent number
US09067871B2

Reaction notes

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