Water → Benzyl 3-allyl-4-oxocyclopentylcarbamate

HRID 590758Notes

Reaction equation

HRID 590758 reaction equation
[CH2:1]=[CH:2][CH2:3][CH:4]1[C:8](=[O:9])[CH:7]=[CH:6][CH2:5]1.[C:10](=[O:20])([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[NH2:11].O.O.O.O.O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[Bi+3].O>ClCCl>[CH2:3]([CH:4]1[C:8](=[O:9])[CH2:7][CH:6]([NH:11][C:10](=[O:20])[O:12][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH2:5]1)[CH:2]=[CH2:1]

Participants

6

Reactant 4

HCID 962WaterHCID 12136Benzyl carbamateHCID 160911Bismuth nitrate pentahydrateHCID 134445455-(Prop-2-en-1-yl)cyclopent-2-en-1-one

Product 1

HCID 67513633Benzyl 3-allyl-4-oxocyclopentylcarbamate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 5-(propene-3-yl)cyclopent-2-enone (4.28 g, 35 mmol) in dichloromethane (15 mL) was treated with benzyl carbamate (10.6 g, 70 mmol) and bismuth trinitrate pentahydrate (2.2 g, 4.5 mmol), stirred rapidly for 18 h, then diluted with dichloromethane (50 mL). The mixture was filtered through Celite® (rinse with dichloromethane) and the filtrate added directly to a silica gel column (˜550 cc). Elution first with 3:2 petroleum ether/dichloromethane afforded recovered starting material (1.01 g), then 4:1 heptane/ethyl acetate gave the subject compound (4.54 g, 47.5% uncorrected yield) as a pale yellow oil. NMR (CDCl3): δ 7.28 (br s, 5 H), 5.55-5.70 (m, 1 H), 5.03 (br s, 2 H), 4.90-5.10 (m, 2 H), 4.75-4.90 (m, 1 H), 4.10-4.30 (m, 1 H), 2.40-2.80 (m, 2 H), 2.15-2.40 (m, 2 H), 1.85-2.15 (m, 3 H). MS (M+Na): 296.0; MS (M−H2O+1): 256.0 (no M+1 visible).

Workup

  1. filtrationThe mixture was filtered through Celite® (rinse with dichloromethane)
  2. additionthe filtrate added directly to a silica gel column (˜550 cc)
  3. washElution first with 3:2 petroleum ether/dichloromethane
  4. customafforded
  5. customrecovered
  6. custom4:1 heptane/ethyl acetate gave
  7. customthe subject compound (4.54 g, 47.5% uncorrected yield) as a pale yellow oil

Sources & evidence

ORD record
ord-dbe0b42c5a31407dbb8d7d6ed01b87d4
Source dataset
uspto-grants-2016_01
Patent number
US09233985B2

Reaction notes

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