1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 86721864, compound

HRID 1049003Notes

Reaction equation

HRID 1049003 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][S:9]([N:12]([C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([Cl:23])[CH:18]=2)[CH2:13][CH:14]([CH3:16])[CH3:15])(=[O:11])=[O:10])=[CH:4][CH:3]=1.CS([N:28]1[CH2:33][CH2:32][NH:31][CH2:30][CH2:29]1)(=O)=O.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)[O:55][C:37]2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=C[C:36]1=2.CC(C)([O-])C.[Na+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:37]([N:28]1[CH2:33][CH2:32][N:31]([C:2]2[CH:7]=[CH:6][C:5]([CH2:8][S:9]([N:12]([C:17]3[CH:22]=[CH:21][CH:20]=[C:19]([Cl:23])[CH:18]=3)[CH2:13][CH:14]([CH3:16])[CH3:15])(=[O:11])=[O:10])=[CH:4][CH:3]=2)[CH2:30][CH2:29]1)(=[O:55])[CH3:36]

Participants

7

Reactant 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 7091611-(Methylsulfonyl)piperazineHCID 23676156Sodium t-butoxideHCID 86721863HCID 86721863, compound

Product 1

HCID 86721864HCID 86721864, compoundYield 134.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of C-(4-bromo-phenyl)-N-(3-chloro-phenyl)-N-isobutyl-methanesulfonamide (150 mg, 36 μmol), 1-methanesulfonylpiperazine (59.2 mg, 361 μmol), Pd2(dba)3 (33 mg, 36 μmol), XantPhos (20.9 mg, 36 μmol), and sodium tert-butoxide (104 mg, 1.08 mmol) in toluene (3 mL) was degassed with nitrogen then heated at 120° C. for 30 minutes in a microwave reactor. Water was added and the reaction extracted with EtOAc, washed with brine, dried with Na2SO4, concentrated and purified by silica gel column chromatography (0-50% EtOAc in cyclohexane) then freeze dried to give the title compound (22.4 mg). 1H NMR (400 MHz, DMSO): δ 7.33-7.34 (m, 4H), 7.22 (d, J=8.5 Hz, 2H), 6.95 (d, J=8.5 Hz, 2H), 4.37 (s, 2H), 3.45 (d, J=7.3 Hz, 2H), 3.22-3.27 (m, 8H), 2.92 (s, 3H), 1.44-1.46 (m, 1H), 0.82 (d, J=6.6 Hz, 6H). LCMS (m/z, Method B) ES+ 499.9 [M+1]+.

Workup

  1. customwas degassed with nitrogen
  2. additionWater was added
  3. extractionthe reaction extracted with EtOAc
  4. washwashed with brine
  5. dry with materialdried with Na2SO4
  6. concentrationconcentrated
  7. custompurified by silica gel column chromatography (0-50% EtOAc in cyclohexane)
  8. customthen freeze dried

Sources & evidence

ORD record
ord-ec42fc08f2c9476fb4f60a49fa4176e4
Source dataset
uspto-grants-2016_07
Patent number
US09382222B2

Reaction notes

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