Cyclopentadiene → HCID 91444739, compound

HRID 735286Notes

Reaction equation

HRID 735286 reaction equation
[C:1]1(=[O:7])[CH2:6][CH2:5][CH2:4][CH:3]=[CH:2]1.[CH:8]1[CH2:12][CH:11]=[CH:10][CH:9]=1.Cl(O)(=O)(=O)=O.C([C@@H]1N[C@H](C2OC(C)=CC=2)N(C)C1=O)C1C=CC=CC=1>O>[C@@H:10]12[CH2:11][C@H:12]([CH:8]=[CH:9]1)[C@@H:3]1[C@@H:2]2[C:1](=[O:7])[CH2:6][CH2:5][CH2:4]1

Participants

6

Reactant 4

HCID 7612CyclopentadieneHCID 135942-Cyclohexen-1-oneHCID 24247Perchloric AcidHCID 11303220(2S,5S)-(-)-5-Benzyl-3-methyl-2-(5-methyl-2-furyl)-4-imidazolidinone

Product 1

HCID 91444739HCID 91444739, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Prepared according to general procedure A from 2-cyclohexen-1-one (58 μL, 0.60 mmol), cyclopentadiene (74 μL, 0.90 mmol), 70% aqueous perchloric acid (10.3 μL, 0.12 mmol), and (2S, 5S)-5-benzyl-3-methyl-2-(5-methyl-furan-2-yl)-imidazolidin-4-one (32.4 mg, 0.15 mmol) in water (150 μL) for 17 hours at 0° C. Purification by silica gel chromatography (5:1 pentane:ether) provided the title compound as a colorless oil in 81% yield (79 mg, 0.49 mmol); 12:1 endo:exo, endo 63% ee. For the purposes of characterization, the endo isomer was separated from the exo isomer by silica gel chromatography. IR (film) 3061, 2961, 2935, 2867, 1701, 1570, 1453, 1406, 1358, 1337, 1315, 1236, 1172, 1115, 1018, 910.6, 823.8, 779.2, 733.6, 561.5 cm−1; 1H NMR (300 MHz, CDCl3) δ 6.15 (dd, J=5.7, 3.0 Hz, 1H, CH═CH), 5.99 (dd, J=5.7, 3.0 Hz, 1H, CH═CH), 3.24 (m, 1H, CHCH═CH), 2.85 (m, 1H, CHCH═CH), 2.66 (m, 2H, CH(H)CO and CHCO), 2.30 (m, 1H, one of CH2CO), 1.79 (m, 4H, CHCHCH2, COCH2CH2 and one of CHCHCH2), 1.42 (ddd, J=8.4, 1.8, 1.8 Hz, 1H, one of CHCH2CH), 1.28 (m, 1H, one of CHCH2CH), 0.73 (m, 1H, one of CHCHCH2); 13C NMR (75 MHz, CDCl3) δ215.7, 137.8, 135.1, 52.0, 48.7, 46.8, 45.5, 41.7, 39.7, 28.4, 22.2; HRMS (CI) exact mass calc'd for (C11H14O) requires m/z 162.1045, found m/z 162.1049. [α]D=+120.6 (c=1.0, CHCl3). Product ratios were determined by GLC analysis (130° C., 23 psi); (1R, 2R, 7R, 8R) endo isomer tr=13.4 min, and (1S, 2S, 7S, 8S) endo isomer tr=13.2 min, exo isomers tr=11.7, 12.3 min.

Workup

  1. customPrepared
  2. customPurification by silica gel chromatography (5:1 pentane:ether)

Sources & evidence

ORD record
ord-8eba259c3c2f4b5ca7b7c23afe4d9cfc
Source dataset
uspto-grants-2009_09
Patent number
US07592463B2

Reaction notes

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