Methanol → 14-Triisopropylsilyloxy-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-ene-2,3,10,16-tetraone

HRID 1885425Notes

Reaction equation

HRID 1885425 reaction equation
C([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](O)([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]([CH3:63])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([O:50][Si](C(C)C)(C(C)C)C(C)C)[CH:46]([O:61][CH3:62])[CH2:45]2)[CH:7]([CH3:64])[CH:6]([O:65][Si:66]([CH:73]([CH3:75])[CH3:74])([CH:70]([CH3:72])[CH3:71])[CH:67]([CH3:69])[CH3:68])[CH2:5][C:4]1=[O:76])C.CO.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.CCCCCC.C(OCC)(=O)C>C(Cl)Cl>[CH:73]([Si:66]([CH:67]([CH3:69])[CH3:68])([CH:70]([CH3:72])[CH3:71])[O:65][CH:6]1[CH2:5][C:4](=[O:76])[CH2:3][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][CH:19]([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]([CH3:63])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([OH:50])[CH:46]([O:61][CH3:62])[CH2:45]2)[CH:7]1[CH3:64])([CH3:74])[CH3:75]

Participants

6

Reactant 4

HCID 887MethanolHCID 521998p-Toluenesulfonic acid monohydrateHCID 21226206Ethyl acetate hexaneHCID 5720084217-Ethyl-1-hydroxy-12-[2'-(4"-triisopropylsilyloxy-3"-methoxycyclohexyl)-1'-methylvinyl]-14-triisopropylsilyloxy-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 8674611214-Triisopropylsilyloxy-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-ene-2,3,10,16-tetraoneYield 92%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

17-Ethyl-1-hydroxy-14-triisopropylsilyloxy-12-[2'-(4"-triisopropylsilyloxy-3"-methoxycyclohexyl)-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 (8.98 g, 8.14 mmol) was slowly added to methanol (70 ml) containing p-toluenesulfonic acid monohydrate (0.70 g). The compound slowly dissolved and after 2 hr. TLC hexane/ethyl acetate (3:1) indicated no starting material was present. The reaction mixture was diluted to 250 ml with MeCl2 and washed with saturated aqueous NaHCO3 (250 ml). The organic layer was separated and the aqueous layer was extracted with additional MeCl2. The combined organic extracts were washed with brine and dried over magnesium sulfate. After evaporation in vacuo, the residue was chromatographed over SiO2 and eluted with MeCl2 /isopropanol (100:3) to yield 17-ethyl-1-hydroxy, 14-triisopropylsilyloxy-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-ene-2,3,10,16-tetraone (6.77 g, 87.9%). Mass Spec: C52H88NO12Si (948.37) FAB+Li:955 (M+Li), 721, 695, 676, 553, 266.

Workup

  1. dissolutionThe compound slowly dissolved and after 2 hr
  2. washwashed with saturated aqueous NaHCO3 (250 ml)
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with additional MeCl2
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over magnesium sulfate
  7. customAfter evaporation in vacuo
  8. customthe residue was chromatographed over SiO2
  9. washeluted with MeCl2 /isopropanol (100:3)

Sources & evidence

ORD record
ord-9a798bdc100343bb9f315be50cc24340
Source dataset
uspto-grants-1992_09
Patent number
US05143918

Reaction notes

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