Acetic Acid → 17-Ethyl-1,14-dihydroxy-12-[2'-(3"-(4'"-chlorophenyloxy)-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

HRID 257689Notes

Reaction equation

HRID 257689 reaction equation
[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:52])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([OH:50])[CH:46]([OH:51])[CH2:45]2)[CH:7]([CH3:53])[CH:6]([OH:54])[CH2:5][C:4]1=[O:55])[CH3:2].C(O)(=O)C.C(O)(=O)C.[Cl:64][C:65]1[CH:70]=[CH:69][C:68]([Bi](C2C=CC(Cl)=CC=2)C2C=CC(Cl)=CC=2)=[CH:67][CH:66]=1.C(O)(=O)C.C(=O)(O)O.ClC1C=CC([Bi](C2C=CC(Cl)=CC=2)C2C=CC(Cl)=CC=2)=CC=1>C(Cl)Cl.C([O-])(O)=O.[Na+].CC([O-])=O.CC([O-])=O.[Cu+2]>[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:52])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([OH:50])[CH:46]([O:51][C:68]3[CH:69]=[CH:70][C:65]([Cl:64])=[CH:66][CH:67]=3)[CH2:45]2)[CH:7]([CH3:53])[CH:6]([OH:54])[CH2:5][C:4]1=[O:55])[CH3:2]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 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 86747380Tri(4-chlorophenyl)bismuth diacetateHCID 86747381Tri(4-chlorophenyl)bismuth carbonate

Product 1

HCID 5719219017-Ethyl-1,14-dihydroxy-12-[2'-(3"-(4'"-chlorophenyloxy)-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

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
40 °C

Procedure

To a stirred mixture of 17-ethyl-1,14-dihydroxy-12-[2'-(3",4"-dihydroxy-cyclohexyl)-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 (150 mg, 0.189 mmol, 1 eq) and Cu(OAc)2 (6.1 mg, 0.033 mmol, 0.17 eq) in CH2Cl2 (2.5 ml) in a round bottom flask equipped with a magnetic stir-bar is added tri(4-chlorophenyl) bismuth diacetate [prepared immediately prior to use by addition of acetic acid (0.075 ml, 1.3 mmol, 6.9 eq) to a suspension of tri(4-chlorophenyl) bismuth carbonate (200 mg, 0.331 mmol, 1.75 eq) in CH2Cl2 (2.5 ml)]. The reaction flask is then fitted with a reflux condensor and the mixture warmed to 40° C. After sufficient time the reaction mixture is cooled, diluted with saturated aqueous NaHCO3 (10 mL) and extracted times with CH2Cl2. The organic extracts were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The product is separated and purified by preparative TLC on silica gel to give 17-ethyl-1,14-dihydroxy-12-[2' -(3"-(4'"-chlorophenyloxy)-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.

Workup

  1. customequipped with a magnetic stir-bar
  2. customprepared immediately
  3. customThe reaction flask is then fitted with a reflux condensor
  4. temperatureAfter sufficient time the reaction mixture is cooled
  5. extractionextracted times with CH2Cl2
  6. dry with materialThe organic extracts were dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe product is separated
  10. custompurified by preparative TLC on silica gel

Sources & evidence

ORD record
ord-8c3c7e787b1a45f99817fbd9a1dbbead
Source dataset
uspto-grants-1993_11
Patent number
US05262533

Reaction notes

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