Methanesulfonate → (+)-1-(2-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphinophenyl)-2-isopropyl-2,3-dihydro-1H-phosphindol

HRID 2084741Notes

Reaction equation

HRID 2084741 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([P:17]([C:25]2[CH:30]=[C:29]([C:31]([CH3:34])([CH3:33])[CH3:32])[C:28]([O:35][CH3:36])=[C:27]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:26]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[PH2:24])[CH:8]=[C:9]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:10]=1[O:11][CH3:12])([CH3:4])([CH3:3])[CH3:2].[CH2:41]([Li])[CH2:42][CH2:43][CH3:44].S([O-])(=O)(=O)C>CCCCCC.C1COCC1>[C:13]([C:9]1[CH:8]=[C:7]([P:17]([C:25]2[CH:30]=[C:29]([C:31]([CH3:34])([CH3:33])[CH3:32])[C:28]([O:35][CH3:36])=[C:27]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:26]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[P:24]2[C:44]3[C:43](=[CH:2][CH:1]=[CH:5][CH:10]=3)[CH2:42][CH:41]2[CH:7]([CH3:8])[CH3:6])[CH:6]=[C:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[C:10]=1[O:11][CH3:12])([CH3:16])([CH3:15])[CH3:14]

Participants

6

Reactant 3

HCID 85257MethanesulfonateHCID 113766522-(Bis(3,5-di(tert-butyl)-4-methoxyphenyl)phosphino)phenylphosphineHCID 178418339Butyllithium2×

Product 1

HCID 22734646(+)-1-(2-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphinophenyl)-2-isopropyl-2,3-dihydro-1H-phosphindolYield 54.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent2×

Procedure

Under a nitrogen atmosphere, 1.0 g (1.72 mmol) of 2-(bis(3,5-di(tert-butyl)-4-methoxyphenyl)phosphino)phenylphosphine was added to 30 ml of THF, followed by cooling with an ice bath. Then, a 1.6M solution of 1.1 ml (1.72 mmol) of n-butyllithium in hexane was added dropwise thereto and, after dropping, the mixture was stirred for 1 hr, a solution of 448 mg (1.72 mmol) of MESYLATE in 10 ml of THF was added dropwise thereto, stirred for 1 hr and, after removing the ice bath, the mixture was stirred for 1 hr at room temperature. Following recooling with an ice bath, a 1.6M solution of 1.6 ml (2.58 mmol) of n-butyllithium in hexane was added dropwise thereto, after dropping, the ice bath was removed and the mixture was stirred overnight at room temperature. 1 ml of water was added to the reaction mixture to quench the reaction and the solvent was distilled off. 10 ml of water was added to the residue and extracted 3 times each with 20 ml of Et2O, and the combined organic layer was washed with 10 ml of water, the solvent was distilled off and the residue was purified by silica gel column chromatography to obtain 337 mg of the title compound. (Yield: 27%)

Workup

  1. temperatureby cooling with an ice bath
  2. stirringstirred for 1 hr
  3. customafter removing the ice bath
  4. stirringthe mixture was stirred for 1 hr at room temperature
  5. customFollowing recooling with an ice bath
  6. customthe ice bath was removed
  7. stirringthe mixture was stirred overnight at room temperature
  8. addition1 ml of water was added to the reaction mixture
  9. customto quench
  10. customthe reaction
  11. distillationthe solvent was distilled off
  12. addition10 ml of water was added to the residue
  13. extractionextracted 3 times each with 20 ml of Et2O
  14. washthe combined organic layer was washed with 10 ml of water
  15. distillationthe solvent was distilled off
  16. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-23bd1c90f22d451b89a80df6bee68cb7
Source dataset
uspto-grants-2004_04
Patent number
US06717016B2

Reaction notes

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