Water → HCID 71059852, compound

HRID 1773436Notes

Reaction equation

[OH:1][C@@H:2]1[C@H:6]2[O:7][C:8]([CH3:11])([CH3:10])[O:9][C@H:5]2[C@H:4](NC(=O)OCC2C=CC=CC=2)[CH2:3]1.[H-].[Na+].Br[CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28].O.[C:33]([O:36][CH2:37][CH3:38])(=[O:35])C>CN(C)C=O>[CH2:37]([O:36][C:33]([C@H:4]1[C@@H:5]2[O:9][C:8]([CH3:10])([CH3:11])[O:7][C@@H:6]2[C@@H:2]([O:1][CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:3]1)=[O:35])[C:38]1[CH:5]=[CH:6][CH:2]=[CH:3][CH:4]=1

Participants

Conditions

Temperature: -30 °C

Procedure

Benzyl (3aS,4R,6S,6aR)-6-hydroxy-2,2-dimethyl-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-ylcarbamate (12.29 g, 39.99 mmol, 1.00 equiv.) was added to a solution of sodium hydride (70%) (1.44 g, 60.00 mmol, 1.05 equiv.) in dimethylformamide (200 mL). The solution was stirred at about −30° C. for about 30 minutes, and then ethyl 2-bromoacetate (7.68 g, 45.99 mmol, 1.20 equiv) was added. The resulting solution was stirred at ambient temperature for about 5.5 hours, and then water was added (500 mL). Following standard extractive workup with ethyl acetate (3×200 mL), the resulting residue was purified by silica gel column chromatography (ethyl acetate: petroleum ether (1:10)) to afford the title product as a colorless solid (0.9 g; yield=69%). 1H NMR (300 MHz, CD3OD) δ: 7.30-7.35 (m, 5H), 5.07 (s, 2H), 4.60 (d, J=5.7 Hz, 1H), 4.51 (d, J=5.7 Hz, 1H), 4.12-4.29 (q, J=16.5 Hz, 2H), 4.10-4.22 (q, J=7.2 Hz, 2H), 4.00 (d, J=5.7 Hz, 1H), 3.92 (J=4.3 Hz, 1H), 2.17-2.19 (m, 1H), 1.84 (d, J=14.7 Hz, 1H), 1.38 (s, 3H), 1.26 (s, 3H), 1.11-1.22 (t, J=7.2 Hz, 3H).

Workup

stirringThe resulting solution was stirred at ambient temperature for about 5.5 hours
customthe resulting residue was purified by silica gel column chromatography (ethyl acetate: petroleum ether (1:10))

Sources & evidence

ORD record: ord-9827a00371184168ab487bc509704018
Source dataset: uspto-grants-2016_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09255104B2

Reaction notes

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