Dimethyl Sulfoxide → (4S,7S,11aR)-7-tert-butoxycarbonylamino-6-oxo-1,3,4,6,7,8,11,11a-octahydro-2H-pyrido[1,2-a]azocine-4-carboxylic Acid Methyl Ester

HRID 722731Notes

Reaction equation

HRID 722731 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[CH2:10][CH2:9][CH2:8][CH:7]([CH2:11]C=C)[N:6]1[C:14](=[O:27])[CH:15]([NH:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH:17]=[CH2:18])=[O:4].CS(C)=O>ClCCl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl>[CH3:1][O:2][C:3]([C@H:5]1[N:6]2[C:14](=[O:27])[C@@H:15]([NH:19][C:20]([O:22][C:23]([CH3:25])([CH3:24])[CH3:26])=[O:21])[CH2:16][CH:17]=[CH:18][CH2:11][C@H:7]2[CH2:8][CH2:9][CH2:10]1)=[O:4]

Participants

5

Reactant 2

HCID 679Dimethyl SulfoxideHCID 696598096-allyl-1-(2-tert-butoxycarbonylamino-pent-4-enoyl)-piperidine-2-carboxylic Acid Methyl Ester

Product 1

HCID 69659542(4S,7S,11aR)-7-tert-butoxycarbonylamino-6-oxo-1,3,4,6,7,8,11,11a-octahydro-2H-pyrido[1,2-a]azocine-4-carboxylic Acid Methyl Ester

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

6-Allyl-1-(2-tert-butoxycarbonylamino-pent-4-enoyl)-piperidine-2-carboxylic acid methyl ester, 40, (1.0 g, 2.6 mmol) is dissolved in dichloromethane (100 mL). Grubbs catalyst (0.5 g, 0.61 mmol) is added and the mixture is heated at reflux for 24 hours. The reaction is cooled and dimethylsulfoxide (2 mL) is added. After 24 hours, the solution is concentrated to a oil, which is purified over silica (ethyl acetate/hexanes) to afford 680 mg of the desired product. 1H NMR (CDCl3) δ 6.02 (d, J=6.6 Hz,1H), 5.61 (m, 1H), 5.21 (m, 1H), 4.93 (ddd, J=6.6, 6.2, 6.2 Hz, 1H), 4.54 (m, 1H), 3.71 (s, 3H), 2.95 (ddd, J=16.2, 5.9, 5.9 Hz, 1H), 2.63 (ddd, J=17.6, 12.0, 5.5 Hz,1H), 2.42 (ddd, J=16.2, 5.8, 5.1 Hz, 1H), 2.34–2.16 (m, 2H), 1.90–1.58 (m, 5H), 1.48 (s, 9H); 13C NMR δ 173.0, 172.5, 155.6, 129.2, 125.0, 79.9, 52.4, 52.0, 51.2, 50.8, 36.6, 34.5, 30.1, 28.8(3C), 26.4, 16.0.

Workup

  1. temperaturethe mixture is heated
  2. temperatureat reflux for 24 hours
  3. temperatureThe reaction is cooled
  4. concentrationthe solution is concentrated to a oil, which
  5. customis purified over silica (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-2910b94ab6c3476c9c05e420614e2bd2
Source dataset
uspto-grants-2006_11
Patent number
US07138395B2

Reaction notes

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