1,3-Dibromobenzene → HCID 71138719, compound

HRID 1914030Notes

Reaction equation

HRID 1914030 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[CH:3]=1.[NH:9]1[CH2:14][CH2:13][S:12](=[O:16])(=[O:15])[CH2:11][CH2:10]1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.C(Cl)Cl.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:8][C:4]1[CH:3]=[C:2]([N:9]2[CH2:14][CH2:13][S:12](=[O:16])(=[O:15])[CH2:11][CH2:10]2)[CH:7]=[CH:6][CH:5]=1

Participants

8

Reactant 4

HCID 79271,3-DibromobenzeneHCID 634876Binap, (A+-)-HCID 6484228Thiomorpholine 1,1-dioxideHCID 23676156Sodium t-butoxide

Product 1

HCID 71138719HCID 71138719, compoundYield 48.4%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1,3-dibromobenzene (242 μL, 2.00 mmol), thiomorpholine 1,1-dioxide (270 mg, 2.00 mmol), Pd2(dba)3 (45.8 mg, 0.0500 mmol), rac-BINAP (96.3 mg, 0.150 mmol) and NaOtBu (231 mg, 2.40 mmol) in toluene was heated at 80° C. for 11 hours under nitrogen. After cooling to room temperature, the mixture was diluted with DCM and filtered through a Celite pad. The combined filtrate and washings were concentrated. The residue was purified by silica gel column chromatography (EtOAc/hexane=90:10→80:20→75:25) to afford desired product (281 mg, 48.4%) as pale yellow solid.

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationfiltered through a Celite pad
  3. concentrationThe combined filtrate and washings were concentrated
  4. customThe residue was purified by silica gel column chromatography (EtOAc/hexane=90:10→80:20→75:25)

Sources & evidence

ORD record
ord-54e12e1baf7c45309f2dd31a9fc35feb
Source dataset
uspto-grants-2013_12
Patent number
US08609688B2

Reaction notes

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