Cesium carbonate → HCID 67085665, compound

HRID 2036747Notes

Reaction equation

HRID 2036747 reaction equation
Br[C:2]1[CH:10]=[CH:9][C:8]2[N:7]([CH:11]([CH3:13])[CH3:12])[C:6]3[CH2:14][CH:15]4[NH:19][CH:18]([C:5]=3[C:4]=2[C:3]=1[C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:17][CH2:16]4.[C:27]1([S:33]([O-:35])=[O:34])[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[Na+].C(=O)([O-])[O-].[Cs+].[Cs+].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>ClCCl.C1(C)C=CC=CC=1>[C:27]1([S:33]([C:2]2[CH:10]=[CH:9][C:8]3[N:7]([CH:11]([CH3:13])[CH3:12])[C:6]4[CH2:14][CH:15]5[NH:19][CH:18]([C:5]=4[C:4]=3[C:3]=2[C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:17][CH2:16]5)(=[O:35])=[O:34])[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2723840Benzenesulfinic acid, sodium saltHCID 67173611HCID 67173611, compound

Product 1

HCID 67085665HCID 67085665, compoundYield 38%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
115 °C

Procedure

To a mixture of the product of step A (270 mg, 0.64 mmol), sodium benzenesulfinate (211 mg, 1.29 mmol), di-palladium-tris(dibenzylideneacetone) (59 mg, 0.06 mmol), cesium carbonate (314 mg, 0.96 mmol) and xantphos (74 mg, 0.12 mmol) under an argon atmosphere was added anhydrous toluene (4 mL). The mixture was heated at 115° C. overnight, cooled to ambient temperature, diluted with dichloromethane and filtered through celite bed. The filtrate was concentrated in vacuo and the residue was purified by flash column chromatography (SiO2, 3:2 hexanes/ethyl acetate) to give tert-butyl 2-phenylsulfonyl-5-isopropyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate (100 mg, 38%) as a yellow solid: 1H NMR (CDCl3, 300 MHz) δ 8.18 (s, 1H), 7.94-7.97 (m, 2H), 7.62 (d, J=8.7 Hz, 1H), 7.43-7.52 (m, 4H), 5.24 (br s, 1H), 4.69 (br s, 1H), 4.46-4.61 (m, 1H), 3.46 (br s, 1H), 2.54 (d, J=15.9 Hz, 1H), 2.25-2.35 (m, 1H), 2.12-2.23 (m, 1H), 1.95 (t, J=9.9 Hz, 1H), 1.56-1.63 (m, 1H), 1.54 (d, J=6.9 Hz, 3H), 1.50 (d, J=6.9 Hz, 3H), 1.33 (s, 9H).

Workup

  1. temperaturecooled to ambient temperature
  2. filtrationfiltered through celite bed
  3. concentrationThe filtrate was concentrated in vacuo
  4. customthe residue was purified by flash column chromatography (SiO2, 3:2 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-90a74a90dd0a42e6ab91ba7acaded6a8
Source dataset
uspto-grants-2013_11
Patent number
US08575186B2

Reaction notes

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