(S)-N-Allyl-N-(1-(2-(cyclopropylthio)-5-nitrophenyl)allyl)-2-methylpropane-2-sulfinamide → (R)-1-((S)-tert-Butylsulfinyl)-2-(2-(cyclopropylthio)-5-nitrophenyl)-2,5-dihydro-1H-pyrrole

HRID 1515550Notes

Reaction equation

HRID 1515550 reaction equation
[CH2:1]([N:4]([CH:11]([C:14]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:15]=1[S:23][CH:24]1[CH2:26][CH2:25]1)C=C)[S@:5]([C:7]([CH3:10])([CH3:9])[CH3:8])=[O:6])[CH:2]=[CH2:3]>C(Cl)Cl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl>[C:7]([S@@:5]([N:4]1[CH2:1][CH:2]=[CH:3][C@@H:11]1[C:14]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:15]=1[S:23][CH:24]1[CH2:26][CH2:25]1)=[O:6])([CH3:8])([CH3:10])[CH3:9]

Participants

4

Reactant 1

HCID 59191805(S)-N-Allyl-N-(1-(2-(cyclopropylthio)-5-nitrophenyl)allyl)-2-methylpropane-2-sulfinamide

Product 1

HCID 59191689(R)-1-((S)-tert-Butylsulfinyl)-2-(2-(cyclopropylthio)-5-nitrophenyl)-2,5-dihydro-1H-pyrrole

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
72 °C

Procedure

A solution of 85C (2.2 g, 5.5 mmol) in CH2Cl2 (200 mL) was degassed by bubbling argon for 8 min. To this solution was added Grubb's catalyst (2nd generation, 380 mg, 0.45 mmol). The mixture was heated at 72° C. for 5.0 h. After removal of solvent, the crude was purified by silica gel column chromatography using gradient EtOAc in hexanes to give 85D as a major product (1.66 g, 82% yield): 1H NMR (400 MHz, CDCl3) δ ppm 0.71-0.80 (m, 2H) 1.15-1.19 (s, 9H) 1.19-1.25 (m, 2H) 2.14-2.22 (m, 1H) 3.78 (dt, J=14.50, 2.64 Hz, 1H) 4.69 (dd, J=14.50, 2.64 Hz, 1H) 5.73 (dd, J=6.15, 2.20 Hz, 1H) 5.85 (dd, J=5.05, 2.42 Hz, 1H) 5.88 (ddd, J=4.06, 2.20, 2.09 Hz, 1H) 7.69 (d, J=8.79 Hz, 1H) 8.06 (dd, J=8.57, 2.42 Hz, 1H) 8.19 (d, J=2.20 Hz, 1H), LC-MS 367 (M+H). 85E was obtained as a minor product (0.31 g, 14% yield): 1H NMR (400 MHz, CDCl3) δ ppm 0.65-0.73 (m, 1H) 0.73-0.82 (m, 1H) 1.01 (s, 9H) 1.17-1.26 (m, 2H) 2.15-2.24 (m, J=7.96, 3.90, 3.74, 3.74 Hz, 1H) 4.36-4.43 (m, 1H) 4.51-4.58 (m, 1H) 5.82 (dd, J=6.15, 2.20 Hz, 1H) 5.87 (d, J=1.76 Hz, 1H) 5.90 (dd, J=5.05, 2.86 Hz, 2H) 7.66 (d, J=8.79 Hz, 1H) 8.06 (dd, J=8.57, 2.42 Hz, 1H) 8.13 (d, J=2.20 Hz, 1H), LC-MS 367 (M+H).

Workup

  1. customby bubbling argon for 8 min
  2. customAfter removal of solvent
  3. customthe crude was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-4f5b7f8885e7434b9aa52a5c89fdab8f
Source dataset
uspto-grants-2012_07
Patent number
US08222453B2

Reaction notes

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