Potassium Carbonate → [(2R)-7-(Methylsulfonyl)-2,3-dihydro-1,4-benzodioxin-2-YL]methanol

HRID 38990

Reaction equation

HRID 38990 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][C@@H:8]([CH2:11][OH:12])[O:7][C:6]=2[CH:13]=1.[CH3:14][S:15]([O-:17])=[O:16].[Na+].N1CCC[C@H]1C(O)=O.C([O-])([O-])=O.[K+].[K+]>CS(C)=O.[Cu]I>[CH3:14][S:15]([C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][C@@H:8]([CH2:11][OH:12])[O:7][C:6]=2[CH:13]=1)(=[O:17])=[O:16]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 145742L-ProlineHCID 2733271Sodium methanesulfinateHCID 66879096(R)-(7-Bromo-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methanol

Product 1

HCID 66878426[(2R)-7-(Methylsulfonyl)-2,3-dihydro-1,4-benzodioxin-2-YL]methanolYield 78.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

Two batches of [(2R)-7-bromo-2,3-dihydro-1,4-benzodioxin-2-yl]methanol (2.2 g, 8.9 mmol), sodium methanesulfinate (85%) (1.6 g, 13.3 mmol), CuI (0.2 g, 0.9 mmol), L-proline (0.2 g, 1.8 mmol) and K2CO3 (0.2 g, 1.8 mmol) in DMSO (20 ml) were heated under microwave radiation at 140° C. for 3 h in nitrogen-flushed vials. Water and EtOAc were added. The water layer was extracted with EtOAc (3×100 ml) and the combined organic phases were washed with LiCl (5%), HCl (1 N) and brine. The resulting solution was dried (Na2SO4) and evaporated to dryness. The residue was purified by flash column chromatography (isooctane/EtOAc) to give the title compound (1.7 g). MS m/z (rel. intensity, 70 eV) 244 (M+, bp), 213 (39), 165 (26), 134 (22), 79 (23).

Workup

  1. customflushed vials
  2. additionWater and EtOAc were added
  3. extractionThe water layer was extracted with EtOAc (3×100 ml)
  4. washthe combined organic phases were washed with LiCl (5%), HCl (1 N) and brine
  5. dry with materialThe resulting solution was dried (Na2SO4)
  6. customevaporated to dryness
  7. customThe residue was purified by flash column chromatography (isooctane/EtOAc)

Sources & evidence

ORD record
ord-4c5db21f63e6492c829c6c16c4269287
Source dataset
uspto-grants-2013_09
Patent number
US08524766B2

Linked notes

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