Peracetic Acid → 17-Ethyl-1,14-dihydroxy-12-[2'-(4"-(4"'-methoxyphenyloxy)-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

HRID 865562Notes

Reaction equation

HRID 865562 reaction equation
COC1C=CC([Bi]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=2)C2C=CC(OC)=CC=2)=CC=1.C(OO)(=O)C.[CH2:31]([CH:33]1[CH:59]=[C:58]([CH3:60])[CH2:57][CH:56]([CH3:61])[CH2:55][CH:54]([O:62][CH3:63])[CH:53]2[O:64][C:49]([OH:68])([CH:50]([CH3:67])[CH2:51][CH:52]2[O:65][CH3:66])[C:48](=[O:69])[C:47](=[O:70])[N:46]2[CH:41]([CH2:42][CH2:43][CH2:44][CH2:45]2)[C:40](=[O:71])[O:39][CH:38]([C:72]([CH3:82])=[CH:73][CH:74]2[CH2:79][CH2:78][CH:77]([OH:80])[CH:76]([OH:81])[CH2:75]2)[CH:37]([CH3:83])[CH:36]([OH:84])[CH2:35][C:34]1=[O:85])[CH3:32].CC(=O)C(=O)CCCCCCC(=O)CCCCCC(=O)CC=CCCCCCCCCC.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(OC)=CC=3)C2)C(C)C(O)CC1=O)C>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C.C1COCC1>[CH2:31]([CH:33]1[CH:59]=[C:58]([CH3:60])[CH2:57][CH:56]([CH3:61])[CH2:55][CH:54]([O:62][CH3:63])[CH:53]2[O:64][C:49]([OH:68])([CH:50]([CH3:67])[CH2:51][CH:52]2[O:65][CH3:66])[C:48](=[O:69])[C:47](=[O:70])[N:46]2[CH:41]([CH2:42][CH2:43][CH2:44][CH2:45]2)[C:40](=[O:71])[O:39][CH:38]([C:72]([CH3:82])=[CH:73][CH:74]2[CH2:79][CH2:78][CH:77]([O:80][C:18]3[CH:19]=[CH:20][C:21]([O:24][CH3:25])=[CH:22][CH:23]=3)[CH:76]([OH:81])[CH2:75]2)[CH:37]([CH3:83])[CH:36]([OH:84])[CH2:35][C:34]1=[O:85])[CH3:32]

Participants

9

Reactant 5

HCID 6585Peracetic AcidHCID 5081858Tris(4-methoxyphenyl)bismuthineHCID 56620592HCID 56620592, compoundHCID 57113032HCID 57113032, 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 5725819417-Ethyl-1,14-dihydroxy-12-[2'-(4"-(4"'-methoxyphenyloxy)-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

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of tri(4-methoxyphenyl)bismuthine (136 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). Each compound was repurified 2× by preparative TLC on silica gel (3:1 hexanes/acetone then 3.5% MeOH/CH2Cl2) affording 23.4 mg of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(4"'-methoxyphenyloxy)-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 28.4 mg of 17-ethyl-1,14-dihydroxy-12-[2'-(3"-(4"'-methoxyphenyloxy)-4"-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. (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. customEach compound was repurified 2× by preparative TLC on silica gel (3:1 hexanes/acetone
  8. custom3.5% MeOH/CH2Cl2) affording 23.4 mg of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(4"'-methoxyphenyloxy)-3"-hydroxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo-22

Sources & evidence

ORD record
ord-06c113ef3f3a42a68798e26dd79caf88
Source dataset
uspto-grants-1996_10
Patent number
US05565560

Reaction notes

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