Boron trifluoride etherate → HCID 22983874, compound

HRID 1263481Notes

Reaction equation

HRID 1263481 reaction equation
B(F)(F)[F:2].CCOCC.N[C:11]1[C:12]([O:30][CH2:31][CH2:32][O:33][CH3:34])=[CH:13][C:14]2[CH2:15][CH2:16][C@@H:17]3[C@@H:26]([C:27]=2[CH:28]=1)[CH2:25][CH2:24][C@@:22]1([CH3:23])[C@H:18]3[CH2:19][CH2:20][C:21]1=[O:29].N(OC(C)(C)C)=O.CCCCC>C(Cl)Cl>[F:2][C:11]1[C:12]([O:30][CH2:31][CH2:32][O:33][CH3:34])=[CH:13][C:14]2[CH2:15][CH2:16][C@@H:17]3[C@@H:26]([C:27]=2[CH:28]=1)[CH2:25][CH2:24][C@@:22]1([CH3:23])[C@H:18]3[CH2:19][CH2:20][C:21]1=[O:29]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8003PentaneHCID 10906Tert-Butyl nitriteHCID 22983872HCID 22983872, compound

Product 1

HCID 22983874HCID 22983874, compoundYield 14%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-15 °C

Procedure

To neat BF3-Et2O (126 μL, 141 mg, 1.00 mmol) at −15° C. under Ar (g) was added a solution of compound 95 (228 mg, 0.66 mmol) in dry CH2Cl2 (4 mL) followed by the dropwise addition t-butyl nitrite (95 μL, 82 mg, 0.80 mmol). This solution was stirred at −15° C. for 10 min then at 0° C. for 1.5 h. Pentane (16 mL) was added to the cold solution and a red gummy solid precipitated. The solvent was decanted and the residue was rinced with cold Et2O (5 mL). The residue was dried under vacuum to give a foamy orange-red solid. This solid was heated under vacuum with a heatgum for 5 min. The residue was purified by flash chromatography (SiO2) using 3:7 to 1:1 EtOAc/Hexanes as eluent to give compound 96 (32 mg, 14%) as a solid. 1H NMR (CDCl3) δ 0.90 (3H, s), 1.25-1.64 (m, 6H), 1.92-2.29 (6H, m), 2.50 (1H, dd, J=18.9 Hz, 8.9 Hz), 2.82 (2H, dd, J=8.4 Hz, J′=3.5 Hz), 3.45 (3H, s), 3.75 (2H, t, J=4.7 Hz), 4.15 (2H, t, J=4.5 Hz), 6.71 (1H, d, J=8.7 Hz), 6.98 (1H, d, J=13.2 Hz); 13C NMR(CDCl3) δ 13.8, 21.5, 25.9, 26.5, 29.0, 29.7, 31.5, 35.8, 38.0, 43.9, 47.9, 50.3, 59.2, 69.2, 71.0, 113.1 (d, J=18.7 Hz), 116.1, 132.6 (d, J=87.0 Hz), 144.5, 149.5, 152.7, 220.6.

Workup

  1. waitat 0° C. for 1.5 h
  2. customa red gummy solid precipitated
  3. customThe solvent was decanted
  4. customThe residue was dried under vacuum
  5. customto give a foamy orange-red solid
  6. temperatureThis solid was heated under vacuum with a heatgum for 5 min
  7. customThe residue was purified by flash chromatography (SiO2)

Sources & evidence

ORD record
ord-a09a18c056014f6884cb4fef117053ab
Source dataset
uspto-grants-2003_04
Patent number
US06541463B1

Reaction notes

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