Benzophenone imine → HCID 86670369, compound

HRID 1972498Notes

Reaction equation

HRID 1972498 reaction equation
Br[C:2]1[S:6][C:5]([S:7]([N:10]2[CH2:15][CH2:14][NH:13][C@@H:12]([CH2:16][CH:17]3[CH2:22][CH2:21][O:20][CH2:19][CH2:18]3)[CH2:11]2)(=[O:9])=[O:8])=[CH:4][CH:3]=1.CC(C)([O-])C.[Na+].[C:29]1([C:35]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[NH:36])[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>C1(C)C=CC=CC=1.C(O[Pd]OC(=O)C)(=O)C.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1>[C:37]1([C:35]([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)=[N:36][C:2]2[S:6][C:5]([S:7]([N:10]3[CH2:15][CH2:14][NH:13][C@@H:12]([CH2:16][CH:17]4[CH2:22][CH2:21][O:20][CH2:19][CH2:18]4)[CH2:11]3)(=[O:9])=[O:8])=[CH:4][CH:3]=2)[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1

Participants

7

Reactant 3

HCID 136809Benzophenone imineHCID 23676156Sodium t-butoxideHCID 66582612HCID 66582612, compound

Product 1

HCID 86670369HCID 86670369, compoundYield 69.1%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

In a sealed vial (3S)-1-((5-bromo-2-thiophenyl)sulfonyl)-3-(tetrahydro-2H-pyran-4-ylmethyl)piperazine (540 mg, 1.32 mmol), diacetoxypalladium (14.81 mg, 0.066 mmol, Strem Chemicals, Newburyport, Mass.), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (XantPhos) (38.2 mg, 0.066 mmol, Strem Chemicals, Newburyport, Mass.), sodium tert-butoxide (279 mg, 2.90 mmol), and diphenylmethanimine (287 mg, 1.58 mmol, Sigma-Aldrich, St. Louis, Mo.) were combined and suspended in toluene (5 mL). Nitrogen gas was bubbled through the solution for 5 min and then the mixture was heated at 100° C. for 16 h. The solution was diluted with EtOAc (20 mL) and then washed with water (15 mL) and brine (15 mL). The organic layer was dried over MgSO4, filtered, and concentrated. The crude material was absorbed onto silica gel and purified via column chromatography (40 g silica gel, 0 to 10% MeOH in CH2Cl2) to give N-(diphenylmethylidene)-5-(((3S)-3-(tetrahydro-2H-pyran-4-ylmethyl)-1-piperazinyl)sulfonyl)-2-thiophenamine (465 mg).

Workup

  1. customNitrogen gas was bubbled through the solution for 5 min
  2. additionThe solution was diluted with EtOAc (20 mL)
  3. washwashed with water (15 mL) and brine (15 mL)
  4. dry with materialThe organic layer was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was absorbed onto silica gel
  8. custompurified via column chromatography (40 g silica gel, 0 to 10% MeOH in CH2Cl2)

Sources & evidence

ORD record
ord-1de7b13efd8646688401e571a4ee8509
Source dataset
uspto-grants-2013_04
Patent number
US08431563B2

Reaction notes

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