Boron trifluoride etherate → HCID 25138942, compound

HRID 1511429Notes

Reaction equation

HRID 1511429 reaction equation
B(F)(F)F.CCOCC.[OH:10][C:11]1[C:20]([O:21][CH3:22])=[C:19]2[C:14]([CH:15]=[C:16]([NH:24][C:25](=[O:34])[O:26][CH2:27][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:17](=[O:23])[O:18]2)=[CH:13][CH:12]=1.ClC(Cl)(Cl)C(=N)O[C@H:39]1[C@@H:44]2[O:45][C:46](=[O:48])[O:47][C@@H:43]2[C@@H:42]([O:49][CH3:50])[C:41]([CH3:52])([CH3:51])[O:40]1.C(N(CC)CC)C>C(Cl)Cl>[CH3:22][O:21][C:20]1[C:11]([O:10][C@H:39]2[C@@H:44]3[O:45][C:46](=[O:48])[O:47][C@@H:43]3[C@@H:42]([O:49][CH3:50])[C:41]([CH3:52])([CH3:51])[O:40]2)=[CH:12][CH:13]=[C:14]2[C:19]=1[O:18][C:17](=[O:23])[C:16]([NH:24][C:25](=[O:34])[O:26][CH2:27][C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)=[CH:15]2

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 25138791HCID 25138791, compoundHCID 67094064(3aR,4S,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxo-tetrahydro-3aH-[1.3]dioxolo[4,5-c]pyran-4-yl 2,2,2-trichloroacetimidate

Product 1

HCID 25138942HCID 25138942, compoundYield 95.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Boron trifluoride etherate (17.3 μL, 0.14 mmol) was added to 23g (157 mg, 0.46 mmol) and (3aR,4S,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxo-tetrahydro-3aH-[1.3]dioxolo[4,5-c]pyran-4-yl 2,2,2-trichloroacetimidate (665 mg, 1.83 mmol) in anhydrous CH2Cl2 (11.5 mL). After stirring at room temperature for 24 hours, triethylamine (150 μL) was added and the solvent was concentrated. The residue was purified via column chromatography (SiO2, 40:1→10:1 CH2Cl2:Acetone) to give 25g as a colorless foam (237 mg, 95%): 1H NMR (CDCl3, 500 MHz) 8.20 (s, 1H), 7.48 (s, 1H), 7.33-7.29 (m, 5H), 7.09 (dd, J=14.2, 8.8 Hz, 2H), 5.72 (d, J=1.8 Hz, 1H), 5.16 (s, 2H), 5.02 (dd, J=7.8, 1.8 Hz, 1H), 4.89 (t, J=7.8 Hz, 1H), 3.88 (s, 3H), 3.52 (s, 3H), 3.21 (d, J=7.8 Hz, 1H), 1.27 (s, 3H) 1.17 (s, 3H); 13C NMR (CDCl3, 125 MHz) 158.0, 153.3, 153.2, 153.1, 149.8, 143.8, 137.1, 135.5, 128.7 (2C), 128.6, 128.3 (2C), 122.7, 122.2, 121.4, 116.1, 113.7, 95.3, 74.7, 72.9, 67.6, 61.9, 60.7, 60.6, 29.7, 29.4; IR (film) νmax 3400, 3319, 2984, 2935, 2359, 1815, 1715, 1609, 1526, 1464, 1383, 1364, 1285, 1213, 1175, 1111, 1063, 968, 764, 737, 700 cm−1; HRMS (ESI+) m/z: [M+Na]+ calcd for C27H27NO11, 564.1482; found, 564.1455.

Workup

  1. concentrationthe solvent was concentrated
  2. customThe residue was purified via column chromatography (SiO2, 40:1→10:1 CH2Cl2:Acetone)

Sources & evidence

ORD record
ord-d1ad5ccc18e54c29989fcc50aa984680
Source dataset
uspto-grants-2012_07
Patent number
US08212012B2

Reaction notes

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