Ethyl Acetate → Benzyl [(3aS,4R,6S,6aR)-6-hydroxy-2,2-dimethyltetrahydro-2H,3aH-cyclopenta[d][1,3]dioxol-4-yl]carbamate

HRID 1773435Notes

Reaction equation

HRID 1773435 reaction equation
[C:1](Cl)(=[O:10])[O:2][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[NH2:12][C@H:13]1[C@@H:17]2[O:18][C:19]([CH3:22])([CH3:21])[O:20][C@@H:16]2[C@@H:15]([OH:23])[CH2:14]1.C(=O)([O-])[O-].[Na+].[Na+].C(OCC)(=O)C>O1CCCC1.O>[OH:23][C@@H:15]1[C@H:16]2[O:20][C:19]([CH3:21])([CH3:22])[O:18][C@H:17]2[C@H:13]([NH:12][C:1](=[O:10])[O:2][CH2:3][C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)[CH2:14]1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 10387Benzyl chloroformateHCID 10352168(3aR,4S,6R,6aS)-6-amino-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-ol

Product 1

HCID 12096654Benzyl [(3aS,4R,6S,6aR)-6-hydroxy-2,2-dimethyltetrahydro-2H,3aH-cyclopenta[d][1,3]dioxol-4-yl]carbamateYield 68%

Reagents, catalysts & solvents 1

HCID 21881883Oxolane--water (1/1)Solvent

Procedure

At about 0° C., benzyl carbonochloridate (18.4 g, 107.86 mmol, 1.05 equiv.) was added to the solution of (3aR,4S,6R,6aS)-6-amino-2,2-dimethyl-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-ol (17.0 g, 98.15 mmol, 1.00 equiv.) and sodium carbonate (20.8 g, 196.24 mmol, 2.00 equiv) in tetrahydrofuran:water (5:1) (600 mL). Standard extractive workup with ethyl acetate (3×200 mL) gave the title product as a white solid (20.5 g; yield=68%). 1H NMR (300 MHz, CDCl3) δ: 7.30-7.39 (m, 5H), 5.20 (s, 2H), 4.60 (d, J=5.4 Hz, 1H), 4.50 (d, J=5.4 Hz, 1H), 4.27 (s, 1H), 4.19 (d, J=5.7 Hz 1H), 2.26 (m, 1H), 1.71 (d, J=14.4 Hz, 1H), 1.47 (s, 3H), 1.28 (s, 3H).

Sources & evidence

ORD record
ord-8ae99873207a4d1782f3bda39eb7e7a8
Source dataset
uspto-grants-2016_02
Patent number
US09255104B2

Reaction notes

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