Boron trifluoride etherate → HCID 67092488, compound

HRID 2059531Notes

Reaction equation

HRID 2059531 reaction equation
C(OC([NH:8][C:9]1([CH2:17][CH2:18][C:19]2[CH:24]=[CH:23][C:22]([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][N:30]3[CH:34]=[C:33]([C:35]4[CH:40]=[CH:39][C:38]([C:41]5[C:42]6[N:46]([C:47]([F:56])([F:55])[N:48]7[C:52]=5[C:51]([CH3:53])=[CH:50][CH:49]7[CH3:54])[C:45]([CH3:57])=[CH:44][C:43]=6[CH3:58])=[CH:37][CH:36]=4)[N:32]=[N:31]3)=[CH:21][CH:20]=2)[CH2:14][O:13]C(C)(C)[O:11][CH2:10]1)=O)(C)(C)C.B(F)(F)F.CCOCC>C(Cl)Cl>[NH2:8][C:9]([CH2:17][CH2:18][C:19]1[CH:24]=[CH:23][C:22]([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][N:30]2[CH:34]=[C:33]([C:35]3[CH:40]=[CH:39][C:38]([C:41]4[C:42]5[N:46]([C:47]([F:56])([F:55])[N:48]6[C:52]=4[C:51]([CH3:53])=[CH:50][CH:49]6[CH3:54])[C:45]([CH3:57])=[CH:44][C:43]=5[CH3:58])=[CH:37][CH:36]=3)[N:32]=[N:31]2)=[CH:21][CH:20]=1)([CH2:10][OH:11])[CH2:14][OH:13]

Participants

4

Reactant 2

HCID 8000Boron trifluoride etherateHCID 67092163HCID 67092163, compound

Product 1

HCID 67092488HCID 67092488, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a cold solution (0° C.) of 21 (40 mg, 50.3 μmol) in dry CH2Cl2 (10 mL) were added 4 Å molecular sieves (0.40 g) and BF3.OEt2 (0.18 g, 1.27 mmol) with vigorous stirring. The mixture was stirred at 0° C., and the reaction was monitored by TLC (hexanes/EtOAc 2:1). On the disappearance of 21 (˜5 h), the reaction was quenched by adding saturated aqueous NaHCO3 solution (10 mL). After the mixture was stirred for 30 min, CH2Cl2 (30 mL) was added. The organic layer was separated and washed with saturated aqueous NaHCO3 solution (20 mL), water (2×20 mL), and brine (2×20 mL). The solution was dried (Na2SO4) and concentrated under vacuum. The residue was purified by chromatography (CH2Cl2/MeOH 9:1) to give 3 (20.1 mg, 61%). 1HNMR δ 7.96 (d, 2H, J=8.4 Hz), 7.84 (s, 1H), 7.34 (d, 2H, J=8.4 Hz), 7.11-7.01 (m, 4H), 5.98 (s, 2H), 4.39 (t, 2H, J=7.2 Hz), 3.85-3.57 (m, 4H), 3.56-3.01 (br s, 4H), 2.61-2.51 (m, 4H), 2.55 (s, 6H), 2.00-1.92 (m, 2H), 1.70-1.56 (m, 2H), 1.43 (s, 6H), 1.46-1.05 (m, 4H); 13C NMR δ 155.6, 147.0, 143.0, 141.2, 139.8, 138.6, 134.7, 131.4, 128.6, 128.5, 128.3, 126.3, 122.5, 121.3, 119.9, 50.4, 35.1, 30.8, 30.3, 29.7, 29.4, 26.0, 14.6, 14.1; 19F NMR δ-146.1 (m). HRMS m/z: calcd for C37H46BF2N6O2 (MH+), 655.3737; found, 655.3746.

Workup

  1. customOn the disappearance of 21 (˜5 h), the reaction was quenched
  2. additionby adding saturated aqueous NaHCO3 solution (10 mL)
  3. stirringAfter the mixture was stirred for 30 min
  4. additionCH2Cl2 (30 mL) was added
  5. customThe organic layer was separated
  6. washwashed with saturated aqueous NaHCO3 solution (20 mL), water (2×20 mL), and brine (2×20 mL)
  7. dry with materialThe solution was dried (Na2SO4)
  8. concentrationconcentrated under vacuum
  9. customThe residue was purified by chromatography (CH2Cl2/MeOH 9:1)

Sources & evidence

ORD record
ord-64aeb80a73a64094aa147a74c5717e9f
Source dataset
uspto-grants-2012_10
Patent number
US08277775B2

Reaction notes

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