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

HRID 2272791Notes

Reaction equation

HRID 2272791 reaction equation
B(F)(F)F.CCOCC.[CH2:10]([C:12]1[C:13]([OH:34])=[CH:14][CH:15]=[C:16]2[C:21]=1[O:20][C:19](=[O:22])[C:18]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[CH:17]2)[CH3:11].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>[CH2:10]([C:12]1[C:13]([O:34][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:14][CH:15]=[C:16]2[C:21]=1[O:20][C:19](=[O:22])[C:18]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[CH:17]2)[CH3:11]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 25138792Benzyl 8-ethyl-7-hydroxy-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 25140543Benzyl 8-ethyl-7-((3aR,4R,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxotetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yloxy)-2-oxo-2H-chromen-3-ylcarbamateYield 51%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Boron trifluoride etherate (19.0 μL, 0.15 mmol) was added to 23h (171 mg, 0.51 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 (183 mg, 0.51 mmol) in anhydrous CH2Cl2 (11.0 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 CH2Cl2:Acetone) to give 25h as a colorless foam (138 mg, 51%): 1H NMR (CD2Cl2, 400 MHz) δ 8.29 (s, 1H), 7.62 (s, 1H), 7.47-7.38 (m, 5H), 7.36 (d, J=8.8 Hz, 1H), 7.19 (d, J=8.4 Hz, 1H), 5.81 (d, J=2.4 Hz, 1H), 5.25 (s, 2H), 5.10 (dd, J=8.0, 2.0 Hz, 1H), 5.02 (t, J=7.8 Hz, 1H), 3.55 (s, 3H), 3.41 (d, J=7.2 Hz, 1H), 2.87 (q, J=7.4 Hz, 2H), 1.42 (s. 3H), 1.28 (s, 3H), 1.21 (t, J=7.4 Hz, 3H); 13C NMR (CD2Cl2, 100 MHz) δ 158.5, 154.8, 153.2, 153.1, 148.4, 136.0, 128.6 (2C), 128.4, 128.1, 125.6, 122.4, 121.5, 120.7, 114.8, 111.4, 94.8, 82.7, 77.9, 77.2, 76.6, 67.3, 60.3, 27.3, 22.3, 16.4, 13.6; IR (film) νmax 3400, 2980, 2937, 2359, 2339, 1817, 1711, 1607, 1524, 1383, 1366, 1227, 1205, 1175, 1101, 1040, 906, 768, 737, 700 cm−1; [M+Na]+ calcd for C28H29NO10, 562.1689. found, 562.1689.

Workup

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

Sources & evidence

ORD record
ord-e631060aa7ca447ab459d3aa7bffc45f
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

Loading…