Benzyl acetate → 7-Ethyl-1-hydroxy-12-[2'-(4"-hydroxy-4"-[benzyloxycarbonylmethyl]-3"-methoxycyclohexyl)-1'-methylvinyl]-14-tert-butyldimethylsilyloxy-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 1079266Notes

Reaction equation

HRID 1079266 reaction equation
[CH3:1][C:2]1C(C)=C(C)[SiH](C)[SiH-](C)(C)C=1.[Na+].[C:14]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)(=[O:16])[CH3:15].C([CH:27]1[CH:53]=[C:52]([CH3:54])[CH2:51][CH:50]([CH3:55])[CH2:49][CH:48]([O:56][CH3:57])[CH:47]2[O:58][C:43]([OH:62])([CH:44]([CH3:61])[CH2:45][CH:46]2[O:59][CH3:60])[C:42](=[O:63])[C:41](=[O:64])[N:40]2[CH:35]([CH2:36][CH2:37][CH2:38][CH2:39]2)[C:34](=[O:65])[O:33][CH:32]([C:66]([CH3:77])=[CH:67][CH:68]2[CH2:73][CH2:72][C:71](=[O:74])[CH:70]([O:75][CH3:76])[CH2:69]2)[CH:31]([CH3:78])[CH:30]([O:79][Si:80]([C:83]([CH3:86])([CH3:85])[CH3:84])([CH3:82])[CH3:81])[CH2:29][C:28]1=[O:87])C>O1CCCC1>[CH2:1]([CH:37]1[CH2:36][CH:35]2[N:40]([C:41](=[O:64])[C:42](=[O:63])[C:43]3([OH:62])[O:58][CH:47]([CH:48]([O:56][CH3:57])[CH2:49][CH:50]([CH3:55])[CH2:51][C:52]([CH3:54])=[CH:53][CH2:27][C:28](=[O:87])[CH2:29][CH:30]([O:79][Si:80]([C:83]([CH3:84])([CH3:85])[CH3:86])([CH3:82])[CH3:81])[CH:31]([CH3:78])[CH:32]([C:66]([CH3:77])=[CH:67][CH:68]4[CH2:73][CH2:72][C:71]([OH:74])([CH2:15][C:14]([O:17][CH2:18][C:19]5[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=5)=[O:16])[CH:70]([O:75][CH3:76])[CH2:69]4)[O:33][C:34]2=[O:65])[CH:46]([O:59][CH3:60])[CH2:45][CH:44]3[CH3:61])[CH2:39][CH2:38]1)[CH3:2]

Participants

5

Reactant 3

HCID 8785Benzyl acetateHCID 5718775817-Ethyl-1-hydroxy-12-[2'-(4"-oxo-3"-methoxycyclohexyl)-1'-methylvinyl]-14-t-butyldimethylsilyloxy-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 131719515Sodium hexamethyldisilamide

Product 1

HCID 570617077-Ethyl-1-hydroxy-12-[2'-(4"-hydroxy-4"-[benzyloxycarbonylmethyl]-3"-methoxycyclohexyl)-1'-methylvinyl]-14-tert-butyldimethylsilyloxy-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 49%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of 20 mL of a 1.0 M solution of sodium hexamethyldisilamide in tetrahydrofuran was cooled to -78° C. in an ice bath under nitrogen. Then a solution of 3.00 g (20 mmole) of benzyl acetate in 10 mL of dry THF was added and the solution was stirred at 0° C. under nitrogen. After 15 min., 4.5 g (5 mmole) of 17-ethyl-1-hydroxy-12-[2'-(4"-oxo-3"-methoxycyclohexyl)-1'-methylvinyl]-14-t-butyldimethylsilyloxy-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 (Example 9) in 10 mL of dry tetrahydrofuran was added dropwise over 5 minutes and the solution was stirred at -78° C. under nitrogen. After 3 h, the reaction was quenched by addition of 2 mL of glacial acetic acid in 10 mL of dry tetrahydrofuran. Diethylether was added and the mixture was partitioned between ether and water and the aqueous layer was washed with ether. The organic fraction was sequentially washed with saturated KHCO3 solution and brine, dried over MgSO4, filtered and concentrated. The oily residue was purified by flash chromatography (silica gel, 6 cm×20 cm) using ethyl acetate-hexane to afford 2.58 g (49%) of the title compound as a colorless foam; MS (FAB) 1060 (M+Li).

Workup

  1. stirringthe solution was stirred at -78° C. under nitrogen
  2. waitAfter 3 h
  3. customthe reaction was quenched by addition of 2 mL of glacial acetic acid in 10 mL of dry tetrahydrofuran
  4. additionDiethylether was added
  5. customthe mixture was partitioned between ether and water
  6. washthe aqueous layer was washed with ether
  7. washThe organic fraction was sequentially washed with saturated KHCO3 solution and brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe oily residue was purified by flash chromatography (silica gel, 6 cm×20 cm)

Sources & evidence

ORD record
ord-abde6938b5aa4dafafc096d1942da575
Source dataset
uspto-grants-1996_08
Patent number
US05550233

Reaction notes

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