HCID 66657196, compound → HCID 66657256, compound

HRID 1726436Notes

Reaction equation

HRID 1726436 reaction equation
[CH2:1]([O:3][C:4]([C@@:6]1([NH:11][C:12]([C@@H:14]2[CH2:18][C@@H:17]([NH:19]C(CC[Si](C)(C)C)=O)[CH2:16][N:15]2[C:28](=[O:45])[C@@H:29]([NH:37][C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH:35]=C)=[O:13])[CH2:8][C@H:7]1[CH:9]=C)=[O:5])[CH3:2]>C(Cl)Cl.CC(OC1C(C=[Ru](Cl)Cl)=CC=CC=1)C.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1>[CH2:1]([O:3][C:4]([C@@:6]12[CH2:8][C@H:7]1[CH:9]=[CH:35][CH2:34][CH2:33][CH2:32][CH2:31][CH2:30][C@H:29]([NH:37][C:38]([O:40][C:41]([CH3:42])([CH3:44])[CH3:43])=[O:39])[C:28](=[O:45])[N:15]1[C@@H:14]([CH2:18][C@@H:17]([NH2:19])[CH2:16]1)[C:12](=[O:13])[NH:11]2)=[O:5])[CH3:2]

Participants

4

Reactant 1

HCID 66657196HCID 66657196, compound

Product 1

HCID 66657256HCID 66657256, compoundYield 69.1%

Reagents, catalysts & solvents 2

HCID 10941020Dichloro(2-isopropoxyphenylmethylene)(tricyclohexylphosphine)rutheniumCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

D A solution of 1-{[1-(2(S)-tert-butoxycarbonylamino-non-8-enoyl)-4(R)-(2-trimethylsilylethyl carbonylamino)-pyrrolidine-2(S)-carbonyl]-amino}-2(S)-vinyl-cyclopropane-1-(R)-carboxylic acid ethyl ester (1.27 g, 1.91 mmol) in methylene chloride (195 ml) was degassed for 1 h by bubbling N2 throughout the solution. Dichloro(o-isopropoxyphenyl-methyene)(tricyclohexylphosphine)ruthenium (II) (0.057 g, 0.096 mmol) was added and the reaction stirred at 40° C. for 16 h. The reaction was concentrated, placed onto silica gel and eluted with 50% ethyl acetate/hexanes. The resulting oil was treated with TBAF (1.0 M in THF, 2.87 ml) and heated to 50° C. for 4 h. The reaction was placed onto silica gel and eluted with 20% methanol/methyene chloride to give a tan solid (0.65 g, 69%). 1H NMR (CDCl3, 400 MHz): δ 1.06-1.66 (m, 17H), 1.85-1.95 (m, 2H), 2.0-2.1 (m, 1H), 2.1-2.2 (m, 1H), 2.2-2.3 (m, 1H), 2.65-2.75 (M, 1H), 3.40 (m, 1H), 3.73-3.83 (m, 2H), 4.08-4.19 (m, 2H), 4.56 (m, 1H), 4.78 (d, J=5.5 Hz, 1H), 5.20 (t, J=8.1 Hz, 1H), 5.34 (d, J=8.1 Hz, 1H), 5.47 (dt, J=4.5, 10.8 Hz, 1H), 7.08 (s, 1H). 493(H+).

Workup

  1. customby bubbling N2 throughout the solution
  2. concentrationThe reaction was concentrated
  3. washeluted with 50% ethyl acetate/hexanes
  4. additionThe resulting oil was treated with TBAF (1.0 M in THF, 2.87 ml)
  5. temperatureheated to 50° C. for 4 h
  6. washeluted with 20% methanol/methyene chloride

Sources & evidence

ORD record
ord-9bc5a60cfbe845519ca43752f752ec18
Source dataset
uspto-grants-2009_02
Patent number
US07491794B2

Reaction notes

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