Methanesulfonyl chloride → 2-(Methanesulfonylamino)phenylboronic acid pinacol ester

HRID 1523990Notes

Reaction equation

HRID 1523990 reaction equation
[CH3:1][C:2]1([CH3:16])[C:6]([CH3:8])([CH3:7])[O:5][B:4]([C:9]2[CH:15]=[CH:14][CH:13]=[CH:12][C:10]=2[NH2:11])[O:3]1.[CH3:17][S:18](Cl)(=[O:20])=[O:19]>N1C=CC=CC=1>[CH3:8][C:6]1([CH3:7])[C:2]([CH3:16])([CH3:1])[O:3][B:4]([C:9]2[CH:15]=[CH:14][CH:13]=[CH:12][C:10]=2[NH:11][S:18]([CH3:17])(=[O:20])=[O:19])[O:5]1

Participants

4

Reactant 2

HCID 31297Methanesulfonyl chlorideHCID 27346522-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

Product 1

HCID 43565252-(Methanesulfonylamino)phenylboronic acid pinacol esterYield 52%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a solution of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (1 g, 5 mmol) in pyridine (20 mL) was added methanesulfonyl chloride (627 mg, 5.5 mmol) and the mixture stirred at rt for 24 hours. The solvent was then removed under reduced pressure, and the resulting residue redissolved in DCM (200 mL), washed with 1 N HCl (1×100 mL) and 20% NaHCO3 (1×100 mL). The organic layer was then isolated, dried (Na2SO4) and concentrated to dryness. The crude product was purified by crystallization from DCM/hexanes to give the title compound (700 mg, 52%). 1H NMR (400 MHz, CDCl3) δ 8.43 (s, 1H), 7.82-7.77 (m, 1H), 7.59 (d, J=8.2, 1H), 7.51-7.43 (m, 1H), 7.17-7.10 (m, 1H), 2.95 (s, 3H), 1.37 (s, 12H).

Workup

  1. customThe solvent was then removed under reduced pressure
  2. dissolutionthe resulting residue redissolved in DCM (200 mL)
  3. washwashed with 1 N HCl (1×100 mL) and 20% NaHCO3 (1×100 mL)
  4. customThe organic layer was then isolated
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated to dryness
  7. customThe crude product was purified by crystallization from DCM/hexanes

Sources & evidence

ORD record
ord-d385e33c5505482e98ba5a0ae4ae3ca4
Source dataset
uspto-grants-2015_07
Patent number
US09079866B2

Reaction notes

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