Boron trifluoride etherate → Benzyl 5-methoxy-7-((3aR,4R,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxotetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yloxy)-8-methyl-2-oxo-2H-chromen-3-ylcarbamate

HRID 2272788Notes

Reaction equation

HRID 2272788 reaction equation
B(F)(F)F.CCOCC.[OH:10][C:11]1[C:20]([CH3:21])=[C:19]2[C:14]([CH:15]=[C:16]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C:17](=[O:22])[O:18]2)=[C:13]([O:34][CH3:35])[CH:12]=1.ClC(Cl)(Cl)C(=N)O[C@H:40]1[C@@H:45]2[O:46][C:47](=[O:49])[O:48][C@@H:44]2[C@@H:43]([O:50][CH3:51])[C:42]([CH3:53])([CH3:52])[O:41]1.C(N(CC)CC)C>C(Cl)Cl>[CH3:35][O:34][C:13]1[CH:12]=[C:11]([O:10][C@H:40]2[C@@H:45]3[O:46][C:47](=[O:49])[O:48][C@@H:44]3[C@@H:43]([O:50][CH3:51])[C:42]([CH3:53])([CH3:52])[O:41]2)[C:20]([CH3:21])=[C:19]2[C:14]=1[CH:15]=[C:16]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[C:17](=[O:22])[O:18]2

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 25140395Benzyl 7-hydroxy-5-methoxy-8-methyl-2-oxo-2H-chromen-3-ylcarbamateHCID 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 25138940Benzyl 5-methoxy-7-((3aR,4R,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxotetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yloxy)-8-methyl-2-oxo-2H-chromen-3-ylcarbamateYield 74%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Boron trifluoride etherate (18.5 μL, 0.15 mmol) was added to 23d (174 mg, 0.49 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 (621 mg, 1.71 mmol) in anhydrous CH2Cl2 (11.0 mL). After stirring at room temperature for 14 hours, triethylamine (150 μL) was added and the solvent was concentrated. The residue was purified via column chromatography (SiO2, 40:1 CH2Cl2:Acetone) to give 25d as a colorless foam (200 mg, 74%): 1H NMR (CDCl3, 500 MHz) δ 8.49 (s, 1H), 7.34-7.27 (m, 5H), 6.67 (s, 1H), 6.60 (s, 1H), 5.69 (s, 2H), 5.16 (d, J=5.3 Hz, 1H), 4.89 (t, J=7.8 Hz, 1H), 4.63 (dd, J=7.9, 2.4 Hz, 1H), 3.83 (s, 3H), 3.37 (s, 3H), 3.15 (d, J=8.0 Hz, 1H), 2.16 (s, 3H), 2.16 (s, 3H), 2.12 (s, 3H); 13C NMR (CDCl3, 125 MHz) δ 158.9, 156.0, 155.2, 154.2, 153.1 (2C), 149.4, 135.7, 128.7 (2C), 128.5, 128.2 (2C), 120.8, 117.4, 106.6, 105.4, 94.6, 94.1, 82.9, 67.4, 60.6, 60.6, 56.1, 56.0, 22.2, 22.0, 7.9; IR (film) νmax 2955, 2924, 2853, 1817, 1713, 1526, 1209, 1105, 1072, 1034, 976, 808 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C28H29NO11, 556.1819. found, 556.1826.

Workup

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

Sources & evidence

ORD record
ord-0ddc22d4a0de463fad7135acc62bfeb9
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

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