Boron trifluoride etherate → P-Toluenesulfonamide

HRID 1955996Notes

Reaction equation

HRID 1955996 reaction equation
[Li]CCCC.BrC1C=CC2OCOC=2C=1.C([Cu])#N.[S:19]([N:29]1CC1)([C:22]1[CH:28]=[CH:27][C:25]([CH3:26])=[CH:24][CH:23]=1)(=[O:21])=[O:20].B(F)(F)F.CCOCC.[NH4+].[Cl-]>C1COCC1>[CH3:26][C:25]1[CH:24]=[CH:23][C:22]([S:19]([NH2:29])(=[O:21])=[O:20])=[CH:28][CH:27]=1

Participants

8

Reactant 6

HCID 8000Boron trifluoride etherateHCID 25517Ammonium ChlorideHCID 758311-Bromo-3,4-(methylenedioxy)benzeneHCID 5612741-(4-Methylbenzenesulfonyl)aziridineHCID 178418339ButyllithiumHCID 178418546HCID 178418546, compound

Product 1

HCID 6269P-ToluenesulfonamideYield 81.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

n-BuLi (1.94 M in hexane, 10 mL) was added to a solution of 6-bromo-1,3-benzodioxol (16.6 mmol) in THF (65 mL) at -78° C. The reaction mixture was stirred for 40 min at -78° C. and CuCN (744 mg, 8.3 mmol) was added. After stirring at -78° C. for 1 h, a solution of aziridine 3 (1.27g, 3.95 mmol) in THF (10 mL) was added, followed by BF3.Et2O (0.40 mL). The reaction mixture was allowed to warm slowly to room temperature while stirring. After addition of saturated aqueous NH4Cl solution (10 mL), the organic layer was separated and the aqueous phase was extracted with ethyl acetate (4×10 mL). The combined organic layers were dried over Na2 SO4 and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, CH2Cl2 /acetone, 12:1) to give tosylamide 5 (552 mg, 32%) as a white solid: mp 75°-76° C.; [α]D22 +44.6° (c 1.16, CHCl3); 1H NMR (200 NMz, CHCl3) δ 7.43 (d, J=8.2 Hz, 2H), 7.09 (d, J=8.2 Hz, 2H), 6.49 (m, 3H), 5.95 (m,3H), 5.76 (dd, J=9.9, 1.6 Hz, 1H), 5.34 (d, J=8.5 Hz, 1H), 4.61 (t, J=4.46 Hz, 1H), 4.13 (dd, j=9.1, 6.0 Hz, 1H), 3.51 (q, J=9.2 Hz, 1H), 3.13 (bd, J=9.8 Hz, 1H), 2.38 (s, 3H), 1.50 (s, 3H), 1.35 (s, 3H); 13C NMR (50 MHz, C6D6) δ 147.9 (C), 146,9 (C), 141.6 (C), 140.6 (C), 135.1 (CH), 135.0 (C), 129.0 (CH), 126.9 (CH), 124.3 (CH), 122.3 (CH), 109.9 (C), 109.2 (CH), 108.4 (CH), 100.7 (CH2), 78.2 (CH), 72.7 (CH), 59.6 (CH) 47.5 (CH), 28.3 (CH3), 26.3 (CH3), 21.1 (CH3); HRMS: calculated for C23H25 O6NS 443.1403, found 443.1416.

Workup

  1. stirringAfter stirring at -78° C. for 1 h
  2. temperatureto warm slowly to room temperature
  3. stirringwhile stirring
  4. customthe organic layer was separated
  5. extractionthe aqueous phase was extracted with ethyl acetate (4×10 mL)
  6. customThe combined organic layers were dried over Na2 SO4
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by column chromatography (silica gel, CH2Cl2 /acetone, 12:1)

Sources & evidence

ORD record
ord-6741b6a3a65d44d79bfb3e2d3fd563a4
Source dataset
uspto-grants-1998_07
Patent number
US05777137

Reaction notes

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