Boron trifluoride etherate → 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-8-phenyl-2H-chromen-3-ylcarbamate

HRID 1511235Notes

Reaction equation

HRID 1511235 reaction equation
B(F)(F)F.CCOCC.[OH:10][C:11]1[C:20]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[C:19]2[C:14]([CH:15]=[C:16]([NH:28][C:29](=[O:38])[O:30][CH2:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)[C:17](=[O:27])[O:18]2)=[CH:13][CH:12]=1.ClC(Cl)(Cl)C(=N)O[C@H:43]1[C@@H:48]2[O:49][C:50](=[O:52])[O:51][C@@H:47]2[C@@H:46]([O:53][CH3:54])[C:45]([CH3:56])([CH3:55])[O:44]1.C(N(CC)CC)C>C(Cl)Cl>[CH3:54][O:53][C@H:46]1[C:45]([CH3:56])([CH3:55])[O:44][C@@H:43]([O:10][C:11]2[C:20]([C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=3)=[C:19]3[C:14]([CH:15]=[C:16]([NH:28][C:29](=[O:38])[O:30][CH2:31][C:32]4[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=4)[C:17](=[O:27])[O:18]3)=[CH:13][CH:12]=2)[C@@H:48]2[O:49][C:50](=[O:52])[O:51][C@H:47]12

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 25140396Benzyl 7-hydroxy-2-oxo-8-phenyl-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 25138941Benzyl 7-((3aR,4R,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxotetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yloxy)-2-oxo-8-phenyl-2H-chromen-3-ylcarbamateYield 99%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Boron trifluoride etherate (14.6 μL, 0.12 mmol) was added to 23f (155 mg, 0.39 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 (560 mg, 1.55 mmol) in anhydrous CH2Cl2 (9.70 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, 100:1→40:1 CH2Cl2:Acetone) to give 25f as a colorless foam (225 mg, 99%): 1H NMR (CD2Cl2, 400 MHz) 8.37 (s, 1H), 7.75-7.73 (m, 2H), 7.60-7.36 (m, 10H), 7.32 (d, J=8.8 Hz, 1H), 5.77 (d, J=1.7 Hz, 1H), 5.26 (s, 2H), 4.76-4.68 (m, 1H), 4.36-4.28 (m, 1H), 3.56 (s, 3H), 3.28 (d, J=7.2 Hz, 1H), 1.37 (s, 3H), 1.31 (s, 3H); 13C NMR (CDCl3, 125 MHz) 157.2, 153.0 (2C), 152.1 (2C), 152.1, 134.4, 129.9, 129.8, 129.4, 127.7 (2C), 127.5, 127.2 (2C), 127.1 (2C), 127.0, 126.3, 121.5 (2C), 120.3, 111.2 (2C), 93.9, 81.9, 66.5, 59.4 (3C), 20.9 (2C); IR (film) νmax 3400, 2959, 2926, 2853, 2359, 2341, 1819, 1715, 1601, 1522, 1381, 1366, 1261, 1215, 1173, 1111, 1059, 970, 800, 700 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C32H29NO10, 588.1870. found, 588.1846.

Workup

  1. concentrationthe solvent was concentrated
  2. customThe residue was purified via column chromatography (SiO2, 100:1→40:1 CH2Cl2:Acetone)

Sources & evidence

ORD record
ord-92502c7fc33f4d77be4bc98927eb50bf
Source dataset
uspto-grants-2012_07
Patent number
US08212011B2

Reaction notes

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