Boron trifluoride etherate → Benzyl 8-benzyl-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 2272789Notes

Reaction equation

HRID 2272789 reaction equation
B(F)(F)F.CCOCC.[CH2:10]([C:17]1[C:18]([OH:39])=[CH:19][CH:20]=[C:21]2[C:26]=1[O:25][C:24](=[O:27])[C:23]([NH:28][C:29](=[O:38])[O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)=[CH:22]2)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.ClC(Cl)(Cl)C(=N)O[C@H:44]1[C@@H:49]2[O:50][C:51](=[O:53])[O:52][C@@H:48]2[C@@H:47]([O:54][CH3:55])[C:46]([CH3:57])([CH3:56])[O:45]1.C(N(CC)CC)C>C(Cl)Cl>[CH2:10]([C:17]1[C:18]([O:39][C@H:44]2[C@@H:49]3[O:50][C:51](=[O:53])[O:52][C@@H:48]3[C@@H:47]([O:54][CH3:55])[C:46]([CH3:57])([CH3:56])[O:45]2)=[CH:19][CH:20]=[C:21]2[C:26]=1[O:25][C:24](=[O:27])[C:23]([NH:28][C:29](=[O:38])[O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)=[CH:22]2)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 25138790Benzyl 8-benzyl-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 25140542Benzyl 8-benzyl-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 39%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Boron trifluoride etherate (7.80 μL, 0.062 mmol) was added to 23e (80.0 mg, 0.21 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 (299 mg, 0.83 mmol) in anhydrous CH2Cl2 (5.20 mL). After stirring at room temperature for 48 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 25e as a colorless foam (47.0 mg, 39%): 1H NMR (CDCl3, 500 MHz) δ 8.22 (s, 1H), 7.46 (s, 1H), 7.35-7.27 (m, 5H), 7.17-7.06 (m, 5H), 6.86 (d, J=10 Hz, 1H), 6.01 (d, J=10 Hz, 1H), 5.65 (d, J=1.6 Hz, 1H), 5.23 (s, 2H), 5.16 (s, 2H), 4.77-4.70 (m, 1H), 4.10 (s, 1H), 3.50 (s, 3H), 3.28 (s, 1H), 3.16 (d, J=7.4 Hz, 1H), 1.25 (s, 3H), 1.18 (s, 3H); 13C NMR (CDCl3, 125 MHz) δ 155.1, 153.2 (2C), 153.1, 148.6 (2C), 139.6 (2C), 128.7, 128.6 (2C), 128.4 (2C), 128.3 (2C), 128.3 (2C), 126.5, 126.2, 123.1, 122.4, 121.7, 117.6, 114.9, 111.5, 94.7, 82.8, 67.6, 60.6 (2C), 29.7, 27.6, 21.9; IR (film) νmax 2926, 2854, 2359, 2341, 1811, 1709, 1607, 1522, 1456, 1381, 1366, 1259, 1209, 1171, 1078, 1049, 968, 766, 700 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C33H31NO10, 602.2026. found, 602.2053.

Workup

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

Sources & evidence

ORD record
ord-7e7113be2fb9456dbc9f3ef454eed89d
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

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