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 → HCID 131718203, compound

HRID 1655775Notes

Reaction equation

HRID 1655775 reaction equation
[C:1]([OH:4])(=[O:3])[CH3:2].[C:5](O)(=[O:7])C.[CH3:9][O:10][C:11]1[CH:12]=[C:13]2[C:18](=[CH:19][CH:20]=1)[CH:17]=[C:16]([Bi](C1C=CC3C(=CC=C(OC)C=3)C=1)[C:22]1[CH:31]=[CH:30][C:29]3[C:24](=[CH:25][CH:26]=[C:27](OC)[CH:28]=3)[CH:23]=1)[CH:15]=[CH:14]2.[CH2:46]([CH:48]1[CH:74]=[C:73]([CH3:75])[CH2:72][CH:71]([CH3:76])[CH2:70][CH:69]([O:77][CH3:78])[CH:68]2[O:79][C:64]([OH:83])([CH:65]([CH3:82])[CH2:66][CH:67]2[O:80][CH3:81])[C:63](=[O:84])[C:62](=[O:85])[N:61]2[CH:56]([CH2:57][CH2:58][CH2:59][CH2:60]2)[C:55](=[O:86])[O:54][CH:53]([C:87]([CH3:97])=[CH:88][CH:89]2[CH2:94][CH2:93][CH:92]([OH:95])[CH:91]([OH:96])[CH2:90]2)[CH:52]([CH3:98])[CH:51]([OH:99])[CH2:50][C:49]1=[O:100])[CH3:47]>C(Cl)Cl.C([O-])(O)=O.[Na+].CC([O-])=O.CC([O-])=O.[Cu+2]>[CH2:46]([CH:48]1[CH:74]=[C:73]([CH3:75])[CH2:72][CH:71]([CH3:76])[CH2:70][CH:69]([O:77][CH3:78])[CH:68]2[O:79][C:64]([OH:83])([CH:65]([CH3:82])[CH2:66][CH:67]2[O:80][CH3:81])[C:63](=[O:84])[C:62](=[O:85])[N:61]2[CH:56]([CH2:57][CH2:58][CH2:59][CH2:60]2)[C:55](=[O:86])[O:54][CH:53]([C:87]([CH3:97])=[CH:88][CH:89]2[CH2:94][CH2:93][CH:92]([O:95][C:16]3[CH:15]=[CH:14][C:13]4[C:18](=[CH:19][CH:20]=[C:11]([O:10][CH3:9])[CH:12]=4)[CH:17]=3)[CH:91]([OH:96])[CH2:90]2)[CH:52]([CH3:98])[CH:51]([OH:99])[CH2:50][C:49]1=[O:100])[CH3:47].[CH2:46]([CH:48]1[CH:74]=[C:73]([CH3:75])[CH2:72][CH:71]([CH3:76])[CH2:70][CH:69]([O:77][CH3:78])[CH:68]2[O:79][C:64]([OH:83])([CH:65]([CH3:82])[CH2:66][CH:67]2[O:80][CH3:81])[C:63](=[O:84])[C:62](=[O:85])[N:61]2[CH:2]([CH2:57][CH2:58][CH2:59][CH2:60]2)[C:1](=[O:4])[O:3][CH:53]([C:87]([CH3:97])=[CH:88][CH:89]2[CH2:94][CH2:93][CH:92]([OH:95])[CH:91]([O:96][C:27]3[CH:26]=[CH:25][C:24]4[C:29](=[CH:30][CH:31]=[C:22]([O:7][CH3:5])[CH:23]=4)[CH:28]=3)[CH2:90]2)[CH:52]([CH3:98])[CH:51]([OH:99])[CH2:50][C:49]1=[O:100])[CH3:47]

Participants

7

Reactant 2

HCID 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-tetraoneHCID 86746579HCID 86746579, compound

Product 2

HCID 131718203HCID 131718203, compoundHCID 131718204HCID 131718204, compound

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of tri-(6-methoxy-2-naphthyl) bismuth diacetate (22 mg, 0.028 mmol, 1 eq) in methylene chloride (2 ml) in a 10 mL round bottom flask equipped with a stir bar 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 (22 mg, 0.028 mmol, 1 eq). To the reaction mixture was added a catalytic amount of Cu(OAc)2 (approximately 20 mg). The reaction flask was fitted with a reflux condenser and the mixture was warmed to 40° C. After 1 hour the mixture was cooled, diluted with saturated aqueous NaHCO3 and extracted 4 times with CH2Cl2. The organic extracts were combined, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The product was isolated by preparative thin layer chromatography on silica gel (eluted with 2:1 hexanes/acetone) to give 7.1 mg of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(6'"-methoxynaphth-2-yloxy)-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 (Rf =0.35) and 9 mg of 17-ethyl-1,14-dihydroxy-12-[2'-(3"-(6'"-methoxy-naphth-2-yloxy)-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 (Rf =0.28). (1H NMR and mass spectral analysis were consistent with the desired structures).

Workup

  1. customThe reaction flask was fitted with a reflux condenser
  2. temperatureAfter 1 hour the mixture was cooled
  3. extractionextracted 4 times with CH2Cl2
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe product was isolated by preparative thin layer chromatography on silica gel (eluted with 2:1 hexanes/acetone)

Sources & evidence

ORD record
ord-79b4802044634e11a85a217724b2f772
Source dataset
uspto-grants-1993_10
Patent number
US05250678

Reaction notes

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