HCID 86643142, compound → HCID 59396844, compound

HRID 1157735Notes

Reaction equation

HRID 1157735 reaction equation
[Li][CH2:2][CH2:3]CC.[CH:6]([C:8]1[CH:28]=[C:27]([C:29]2[C:38]3[C:33](=[CH:34][C:35]([O:39][CH3:40])=[CH:36][CH:37]=3)[O:32][C:31](=[O:41])[CH:30]=2)[CH:26]=[CH:25][C:9]=1[O:10][C:11]1[CH:12]=[C:13]([C@@:17]2([CH3:24])[O:21][C:20](=[O:22])[NH:19][C:18]2=[O:23])[CH:14]=[CH:15][CH:16]=1)=O>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.C1COCC1>[CH3:40][O:39][C:35]1[CH:34]=[C:33]2[C:38]([C:29]([C:27]3[CH:26]=[CH:25][C:9]([O:10][C:11]4[CH:12]=[C:13]([C@@:17]5([CH3:24])[O:21][C:20](=[O:22])[NH:19][C:18]5=[O:23])[CH:14]=[CH:15][CH:16]=4)=[C:8]([CH2:6][CH2:2][CH3:3])[CH:28]=3)=[CH:30][C:31](=[O:41])[O:32]2)=[CH:37][CH:36]=1

Participants

5

Reactant 2

HCID 86643142HCID 86643142, compoundHCID 178418339Butyllithium

Product 1

HCID 59396844HCID 59396844, compound

Reagents, catalysts & solvents 2

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-75 °C

Procedure

To a suspension of ethyltriphenylphophonium bromide (0.56 g, 1.5 mmol) in THF (8 mL) cooled at −75° C. was added n-BuLi (1.6 M in hexane, 1.0 mL). To the resulting orange solution was added the product from step 2 (0.24 g, 0.50 mol) in THF (1.0 mL). The reaction mixture was gradually warmed to 25° C. and quenched with acetic acid (0.1 mL). The solvent was removed and the residue was taken up in diethyl ether and filtered through a short column of silica gel. The filtrated was concentrated and the residue was dissolved in THF-t-BuOH (1:1, v/v) (10 mL). The solution was stirred in the presence of Rh(PPh3)3Cl (40 mg) under hydrogen (45 psi) for 18 h. The reaction mixture was concentrated and the residue was purified by preparative HPLC on a RP-18 column using 10-100% acetonitrile in water gradient solvent system modified with 0.1% trifluoroacetic acid to give the title compound.

Workup

  1. temperatureThe reaction mixture was gradually warmed to 25° C.
  2. customquenched with acetic acid (0.1 mL)
  3. customThe solvent was removed
  4. filtrationfiltered through a short column of silica gel
  5. concentrationThe filtrated was concentrated
  6. dissolutionthe residue was dissolved in THF-t-BuOH (1:1
  7. concentrationThe reaction mixture was concentrated
  8. customthe residue was purified by preparative HPLC on a RP-18 column

Sources & evidence

ORD record
ord-7651398b174546fe803a9f949f039df7
Source dataset
uspto-grants-2010_10
Patent number
US07807692B2

Reaction notes

Loading…