Potassium Phosphate, Tribasic → (3-Bromophenyl)(3'-(dibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)diphenylsilane

HRID 403145Notes

Reaction equation

HRID 403145 reaction equation
[CH:1]1[C:9]2[C:8]3[CH:10]=[CH:11][CH:12]=[CH:13][C:7]=3[S:6][C:5]=2[C:4]([C:14]2[CH:15]=[C:16](B3OC(C)(C)C(C)(C)O3)[CH:17]=[CH:18][CH:19]=2)=[CH:3][CH:2]=1.Br[C:30]1[CH:31]=[C:32]([Si:36]([C:49]2[CH:54]=[CH:53][CH:52]=[C:51]([Br:55])[CH:50]=2)([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH:33]=[CH:34][CH:35]=1.COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C(C)=CC=CC=1.O.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]>[Br:55][C:51]1[CH:50]=[C:49]([Si:36]([C:32]2[CH:31]=[C:30]([C:16]3[CH:17]=[CH:18][CH:19]=[C:14]([C:4]4[C:5]5[S:6][C:7]6[CH:13]=[CH:12][CH:11]=[CH:10][C:8]=6[C:9]=5[CH:1]=[CH:2][CH:3]=4)[CH:15]=3)[CH:35]=[CH:34][CH:33]=2)([C:43]2[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=2)[C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[CH:54]=[CH:53][CH:52]=1

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 297508Bis(3-bromophenyl)diphenylsilaneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 595753552-(3-(Dibenzo[b,d]thiophen-4-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 86674048(3-Bromophenyl)(3'-(dibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)diphenylsilaneYield 30.6%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 7237O-XyleneSolvent

Procedure

A mixture solution of 2-(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.0 g, 15.53 mmol), bis(3-bromophenyl)diphenylsilane (19.19 g, 38.8 mmol), Pd2(dba)3 (0.28 g, 0.31 mmol), SPhos (0.26 g, 0.62 mmol) and K3PO4 (3.30 g, 15.53 mmol) in xylene (150 mL) and water (15 mL) was refluxed under nitrogen at 120° C. overnight. After cooling to room temperature, the reaction mixture was quenched with water, extracted with DCM, washed with brine and water, and dried over Na2SO4. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with hexane:DCM (9.5:0.5 to 9:1, v/v) as eluent. The crude product was dissolved in DCM, precipitated with methanol, and filtered to yield (3-bromophenyl)(3′-(dibenzo[b,d]thiophen-4-yl)-[1,1′-biphenyl]-3-yl)diphenylsilane (3.2 g, 30.6%) as a white powder.

Workup

  1. customthe reaction mixture was quenched with water
  2. extractionextracted with DCM
  3. washwashed with brine and water
  4. dry with materialdried over Na2SO4
  5. customUpon evaporation of the solvent
  6. customthe residue was purified by column chromatography on silica gel with hexane:DCM (9.5:0.5 to 9:1
  7. dissolutionThe crude product was dissolved in DCM
  8. customprecipitated with methanol
  9. filtrationfiltered

Sources & evidence

ORD record
ord-08dc7908259c401badcab96de10882c3
Source dataset
uspto-grants-2014_06
Patent number
US08748012B2

Reaction notes

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