Peracetic Acid → HCID 131718206, compound

HRID 1655778Notes

Reaction equation

HRID 1655778 reaction equation
[Si](OC1C=CC([Bi]([C:30]2[CH:35]=[CH:34][C:33]([O:36][Si:37]([C:40](C)(C)C)([CH3:39])C)=[CH:32][CH:31]=2)C2C=CC(O[Si](C(C)(C)C)(C)C)=CC=2)=CC=1)(C(C)(C)C)(C)C.C(OO)(=O)C.[CH2:49]([CH:51]1[CH:77]=[C:76]([CH3:78])[CH2:75][CH:74]([CH3:79])[CH2:73][CH:72]([O:80][CH3:81])[CH:71]2[O:82][C:67]([OH:86])([CH:68]([CH3:85])[CH2:69][CH:70]2[O:83][CH3:84])[C:66](=[O:87])[C:65](=[O:88])[N:64]2[CH:59]([CH2:60][CH2:61][CH2:62][CH2:63]2)[C:58](=[O:89])[O:57][CH:56]([C:90]([CH3:100])=[CH:91][CH:92]2[CH2:97][CH2:96][CH:95]([OH:98])[CH:94]([OH:99])[CH2:93]2)[CH:55]([CH3:101])[CH:54]([OH:102])[CH2:53][C:52]1=[O:103])[CH3:50].[CH2:104]([CH:106]1[CH:132]=C(C)CC(C)CC(OC)C2OC(O)(C(C)CC2OC)C(=O)C(=O)N2C(CCCC2)C(=O)OC(C(C)=CC2CCC(OC3C=CC(O[Si](C(C)(C)C)(C)C)=CC=3)C(O)C2)C(C)C(O)C[C:107]1=O)C.C(C1C=C(C)CC(C)CC(OC)C2OC(O)(C(C)CC2OC)C(=O)C(=O)N2C(CCCC2)C(=O)OC(C(C)=CC2CCC(O)C(OC3C=CC(O[Si](C(C)(C)C)(C)C)=CC=3)C2)C(C)C(O)CC1=O)C>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C.C1COCC1>[CH2:49]([CH:51]1[CH2:77][C:76]([CH3:78])=[CH:75][CH:74]([CH3:79])[CH2:73][CH:72]([O:80][CH3:81])[CH:71]2[O:82][C:67]([OH:86])([CH:68]([CH3:85])[CH2:69][CH:70]2[O:83][CH3:84])[C:66](=[O:87])[C:65](=[O:88])[N:64]2[CH:59]([CH2:60][CH2:61][CH2:62][CH2:63]2)[C:58](=[O:89])[O:57][CH:56]([C:90]([CH3:100])=[CH:91][CH:92]2[CH2:97][CH2:96][CH:95]([O:98][C:32]3[CH:31]=[CH:30][C:35]([C:106]([CH3:132])([CH3:107])[CH3:104])=[CH:34][C:33]=3[O:36][SiH:37]([CH3:39])[CH3:40])[CH:94]([OH:99])[CH2:93]2)[CH:55]([CH3:101])[CH:54]([OH:102])[CH2:53][C:52]1=[O:103])[CH3:50]

Participants

9

Reactant 5

HCID 6585Peracetic AcidHCID 21469202HCID 21469202, compoundHCID 57110967HCID 57110967, compoundHCID 57193466HCID 57193466, compoundHCID 5720384517-Ethyl-1,14-dihydroxy-12-[2'(3",4"-dihydroxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraone

Product 1

HCID 131718206HCID 131718206, compound

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of tri(4-tert-butyldimethylsilyloxyphenyl)bismuthine (213 mg., 0.257 mmol., 2 eq.) in methylene chloride (4 mL.) was added peracetic acid (0.054 mL., 0.257 mmol., 2 eq. 32% solution in dilute acetic acid). To this stirred solution was added 17-ethyl-1,14-dihydroxy-12-[2'-(3",4"-dihydroxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (100 mg., 0.126 mmol., 1 eq.), THF (0.5 mL.), and copper (II) acetate (7 mg., 0.038 mmol., 0.3 eq.). The mixture was allowed to stir for 7 days. The reaction was quenched with saturated aqueous NaCl plus 2 drops 2N HCl and extracted 4× with methylene chloride. The organic extracts were combined, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The products were separated by preparative TLC on silica gel (2:1 hexanes/acetone) affording 41.9 mg. of 17-ethyl-1,14-dihydroxy-12-[2'-(4"(4'"-tert-butyldimethylsilyloxyphenyloxy)-3"-hydroxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone and 42.5 mg. of 17-ethyl-1,14-dihydroxy-12-[2'-(3"-(4'"-tert-butyldimethylsilyloxyphenyloxy)-4"-hydroxycylohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo [22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone. (1H NMR and mass spectral analysis were consistent with the desired structures).

Workup

  1. customThe reaction was quenched with saturated aqueous NaCl plus 2 drops 2N HCl
  2. extractionextracted 4× with methylene chloride
  3. dry with materialdried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe products were separated by preparative TLC on silica gel (2:1 hexanes/acetone)
  7. customaffording 41.9 mg

Sources & evidence

ORD record
ord-965e5a60116e49bc9b48df1411f92f80
Source dataset
uspto-grants-1993_10
Patent number
US05250678

Reaction notes

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