Phosphine → HCID 178450836, compound

HRID 1518387Notes

Reaction equation

HRID 1518387 reaction equation
Br[C:2]1[C:3]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])=[N:4][C:5]([N:8]2[CH2:17][CH2:16][C:15]3[C:10](=[C:11]([C:18](=[O:37])/[N:19]=[C:20]4\[S:21][C:22]5[CH:36]=[CH:35][CH:34]=[CH:33][C:23]=5[N:24]\4[CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[CH:12]=[CH:13][CH:14]=3)[CH2:9]2)=[CH:6][CH:7]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.[Br-].[O:75]1[CH2:79][CH2:78][O:77][CH:76]1[CH2:80][CH2:81][Zn+].P>C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[O:75]1[CH2:79][CH2:78][O:77][CH:76]1[CH2:80][CH2:81][C:2]1[C:3]([C:38]([O:40][C:41]([CH3:43])([CH3:42])[CH3:44])=[O:39])=[N:4][C:5]([N:8]2[CH2:17][CH2:16][C:15]3[C:10](=[C:11]([C:18](=[O:37])/[N:19]=[C:20]4\[S:21][C:22]5[CH:36]=[CH:35][CH:34]=[CH:33][C:23]=5[N:24]\4[CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:31])([CH3:32])[CH3:30])[CH:12]=[CH:13][CH:14]=3)[CH2:9]2)=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 24404PhosphineHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 178419780HCID 178419780, compound2×HCID 178450835HCID 178450835, compound

Product 1

HCID 178450836HCID 178450836, compoundYield 89.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst2×HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of compound 94C (2.97 g, 4.27 mmol), dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (0.35 g, 0.854 mmol) and palladium acetate (0.096 g, 0.427 mmol) in THF (20 mL) was stirred at room temperature for 5 min. To this solution was added 0.5 M (2-(1,3-dioxolan-2-yl)ethyl)zinc(II) bromide (17.08 mL, 8.54 mmol) dropwise at room temperature. The reaction was stirred overnight. To the solution were added 2′,6′-dimethoxybiphenyl-2-yl)phosphine (170 mg), palladium acetate (42 mg) and (2-(1,3-dioxolan-2-yl)ethyl)zinc(II) bromide (15 mL). The resulting mixture was stirred for another 6 hours and concentrated. The residue was loaded on a silica gel column and eluted with 7:3/hexanes:EtOAc to afford 2.75 g of desired product 94D which is a mixture of two isomers. APCI (+) LC/MS: 717 (M+H)+.

Workup

  1. stirringThe reaction was stirred overnight
  2. stirringThe resulting mixture was stirred for another 6 hours
  3. concentrationconcentrated
  4. washeluted with 7:3/hexanes

Sources & evidence

ORD record
ord-e47832d973a648c1848c92fcccb50bce
Source dataset
uspto-grants-2012_07
Patent number
US08232273B2

Reaction notes

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