1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 86609636, compound

HRID 1162020Notes

Reaction equation

HRID 1162020 reaction equation
I[C:2]1[C:10]2[O:9][CH:8]=[CH:7][C:6]=2[CH:5]=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=1.[NH:14]1[CH2:19][CH2:18][CH:17]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:16][CH2:15]1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CC(C)([O-])C.[Na+]>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].C1(C)C(C)=CC=CC=1>[C:23]([O:22][C:21](=[O:27])[NH:20][CH:17]1[CH2:18][CH2:19][N:14]([C:2]2[C:10]3[O:9][CH:8]=[CH:7][C:6]=3[CH:5]=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=2)[CH2:15][CH2:16]1)([CH3:26])([CH3:24])[CH3:25]

Participants

7

Reactant 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 7238334-(N-Boc-amino)piperidineHCID 21864764HCID 21864764, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 86609636HCID 86609636, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 7237O-XyleneSolvent

Conditions

Temperature
120 °C

Procedure

Xylene (200 mL) was added to 7-iodo-5-nitro-1-benzofuran (2.78 g, 9.61 mmol), tert-butyl piperidin-4-ylcarbamate (2.31 g, 12.0 mmol), Pd2(dba)3 (0.22 g, 0.24 mmol), Xantphos (0.56 g, 0.96 mmol) and sodium tert-butoxide (1.29 g, 13.0 mmol). The mixture was heated at 120° C. with stirring for 16 h. The reaction mixture was allowed to reach room temperature, filtered through a pad of Celite, and concentrated in vacuo. The crude product was purified by flash chromatography, using DCM as eluent, to afford 1.03 g (84%) of the title product. HPLC 94%, RT: 2.770 (System B; 10-97% MeCN over 3 min). 1H NMR (270 MHz, methanol-d4) δ ppm 1.45 (s, 9H) 1.62-1.72 (m, 2H) 1.75-2.03 (m, 2H) 2.94-3.02 (m, 2H) 3.55-3.57 (m, 1H) 3.88-3.93 (m, 2H) 7.01 (d, J=2.23 Hz, 1H) 7.64 (d, J=2.23 Hz, 1H) 7.93 (d, J=2.23 Hz, 1H) 8.13 (d, J=2.23 Hz, 1H). LC-MS 362 (M+H)+.

Workup

  1. customto reach room temperature
  2. filtrationfiltered through a pad of Celite
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-d45ab57c2da74a9888e9327650b0f158
Source dataset
uspto-grants-2010_10
Patent number
US07820675B2

Reaction notes

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