Potassium Acetate → 3-Methyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)thietane 1,1-dioxide

HRID 929261Notes

Reaction equation

HRID 929261 reaction equation
[BH:1]([O:3]BO)[OH:2].O[C:7]([C:10](O)([CH3:12])[CH3:11])([CH3:9])[CH3:8].C([O-])(=O)C.[K+].Br[C:20]1[CH:25]=[CH:24][C:23]([C:26]2([CH3:32])[CH2:29][S:28](=[O:31])(=[O:30])[CH2:27]2)=[CH:22][CH:21]=1>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[CH3:32][C:26]1([C:23]2[CH:24]=[CH:25][C:20]([B:1]3[O:3][C:10]([CH3:12])([CH3:11])[C:7]([CH3:9])([CH3:8])[O:2]3)=[CH:21][CH:22]=2)[CH2:29][S:28](=[O:31])(=[O:30])[CH2:27]1

Participants

6

Reactant 3

HCID 517044Potassium AcetateHCID 124571823-(4-Bromophenyl)-3-methylthietane 1,1-dioxideHCID 178459140HCID 178459140, compound

Product 1

HCID 900421873-Methyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)thietane 1,1-dioxide

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

Step D To pinacol diboronate (250 mg, 0.986 mmol), potassium acetate (242 mg, 2.466 mmol) and PdCl2(dppf)-CH2Cl2 adduct (67 mg, 0.082 mmol) in a thick-walled tube was added a solution of 3-(4-bromophenyl)-3-methylthietane 1,1-dioxide (226 mg, from Step C) in DMF (5 ml). The tube was flushed with N2, then capped and heated to 90° C. for 4 hours. Then the reaction was cooled to RT and diluted with EtOAc (30 ml) and water (20 ml). The aqueous layer was separated and extracted with EtOAc (25 ml). The combined organic layers were washed with water (50 ml), dried (Na2SO4), filtered and concentrated. The resulting crude material was purified by Isco™ system, 40 g gold cartridge, 40 ml flow rate, gradient—0/100 (1 min) to 50/50 (19 min) to 50/50 (21 min—total run time) of EtOAc/hexanes. The fractions containing the product were combined and concentrated to provide 3-methyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)thietane 1,1-dioxide as a white solid.

Workup

  1. customThe tube was flushed with N2
  2. customcapped
  3. temperatureThen the reaction was cooled to RT
  4. additiondiluted with EtOAc (30 ml) and water (20 ml)
  5. customThe aqueous layer was separated
  6. extractionextracted with EtOAc (25 ml)
  7. washThe combined organic layers were washed with water (50 ml)
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe resulting crude material was purified by Isco™ system, 40 g gold cartridge, 40 ml flow rate, gradient—0/100 (1 min) to 50/50 (19 min) to 50/50 (21 min—total run time) of EtOAc/hexanes
  12. additionThe fractions containing the product
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-a768ca25f8bc4002b5a65b7cd1c0aca4
Source dataset
uspto-grants-2016_03
Patent number
US09290517B2

Reaction notes

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