Peracetic Acid → 17-Ethyl-20-fluoro-1,14-dihydroxy-12-[2'-(4"-(6'"-tert-butyldimethylsilyloxynaphth-2-yloxy)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetra-methyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]-octacos-18-ene-2,3,10,16-tetraone

HRID 2082628Notes

Reaction equation

HRID 2082628 reaction equation
[Si](OC1C=C2C(=CC=1)C=C([Bi](C1C=CC3C(=CC=C(O[Si](C(C)(C)C)(C)C)C=3)C=1)C1C=[CH:28][C:27]3[C:22](=[CH:23][CH:24]=[C:25]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])(C)[CH3:32])[CH:26]=3)C=1)C=C2)(C(C)(C)C)(C)C.[C:56](OO)(=O)C.[CH2:61]1[CH2:65]OC[CH2:62]1.[CH2:66]([CH:68]1[CH:94]=[C:93]([CH3:95])[CH:92]([F:96])[CH:91]([CH3:97])[CH2:90][CH:89]([O:98][CH3:99])[CH:88]2[O:100][C:84]([OH:104])([CH:85]([CH3:103])[CH2:86][CH:87]2[O:101][CH3:102])[C:83](=[O:105])[C:82](=[O:106])[N:81]2[CH:76]([CH2:77][CH2:78][CH2:79][CH2:80]2)[C:75](=[O:107])[O:74][CH:73]([C:108]([CH3:119])=[CH:109][CH:110]2[CH2:115][CH2:114][CH:113]([OH:116])[CH:112]([O:117][CH3:118])[CH2:111]2)[CH:72]([CH3:120])[CH:71]([OH:121])[CH2:70][C:69]1=[O:122])[CH3:67]>C(Cl)Cl.CC([O-])=O.CC([O-])=O.[Cu+2]>[CH2:66]([CH:68]1[CH:94]=[C:93]([CH3:95])[CH:92]([F:96])[CH:91]([CH3:97])[CH2:90][CH:89]([O:98][CH3:99])[CH:88]2[O:100][C:84]([OH:104])([CH:85]([CH3:103])[CH2:86][CH:87]2[O:101][CH3:102])[C:83](=[O:105])[C:82](=[O:106])[N:81]2[CH:76]([CH2:77][CH2:78][CH2:79][CH2:80]2)[C:75](=[O:107])[O:74][CH:73]([C:108]([CH3:119])=[CH:109][CH:110]2[CH2:115][CH2:114][CH:113]([O:116][C:61]3[CH:65]=[CH:28][C:27]4[C:22](=[CH:23][CH:24]=[C:25]([O:30][Si:31]([C:34]([CH3:35])([CH3:37])[CH3:36])([CH3:32])[CH3:56])[CH:26]=4)[CH:62]=3)[CH:112]([O:117][CH3:118])[CH2:111]2)[CH:72]([CH3:120])[CH:71]([OH:121])[CH2:70][C:69]1=[O:122])[CH3:67]

Participants

7

Reactant 4

HCID 6585Peracetic AcidHCID 8028TetrahydrofuranHCID 21469196Tri(6-tert-butyldimethylsilyloxynaphth-2-yl)bismuthineHCID 5702442717-Ethyl-20-fluoro-1,14-dihydroxy-12-[2'-(4"-hydroxy-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13, 19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo-[22.3.1.04,9]octacos-18-ene2,3,10,16-tetraone

Product 1

HCID 5710832717-Ethyl-20-fluoro-1,14-dihydroxy-12-[2'-(4"-(6'"-tert-butyldimethylsilyloxynaphth-2-yloxy)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetra-methyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]-octacos-18-ene-2,3,10,16-tetraone

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

To a stirred solution of tris(6-tert-butyldimethylsilyloxynaphth-2-yl)bismuthine (100 mg, 0.215 mmol) in CH2Cl2 (4 mL) is added peracetic acid (0.05 mL, 0.238 mmol, 32 wt % in dilute acetic acid). To this stirred solution is added THF (1 mL), 17-ethyl-20-fluoro-1,14-dihydroxy-12-[2'-(4"-hydroxy-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13, 19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo-[22.3.1.04,9 ]octacos-18-ene2,3,10,16-tetraone (100 mg, 0.126 mmol) and Cu(OAc)2 (catalytic amount). The flask is fitted with a reflux condenser and the mixture is heated to 40° C. for 2 hours. The mixture is allowed to cool and was stirred 72 hours. The reaction is quenched with saturated aqueous NaHCO3 and extracted 4× with CH2Cl2. The organic extracts are combined and dried over anhydrous Na2SO4. The mixture is filtered and concentrated in vacuo. The products are isolated by preparative TLC on silica gel to afford the title compound.

Workup

  1. customThe flask is fitted with a reflux condenser
  2. temperatureto cool
  3. customThe reaction is quenched with saturated aqueous NaHCO3
  4. extractionextracted 4× with CH2Cl2
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationThe mixture is filtered
  7. concentrationconcentrated in vacuo
  8. customThe products are isolated by preparative TLC on silica gel

Sources & evidence

ORD record
ord-f22e648b5aa448089dd965911299c1f7
Source dataset
uspto-grants-1993_02
Patent number
US05189042

Reaction notes

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