Ethanol → HCID 54410145, compound

HRID 375755Notes

Reaction equation

HRID 375755 reaction equation
[Si:1]([O:8][C:9]1[C:24]2[CH2:23][S:22][CH2:21][C@@H:20]([C:25]([O:27][CH3:28])=[O:26])[NH:19][C:18](=[O:29])[C@@H:17]([NH:30][C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:16][O:15][C:14](=[O:38])[C:13]=2[C:12]([CH3:39])=[C:11]([O:40][CH3:41])[CH:10]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:42](O)C>C(OCC)(=O)C.CC([O-])C.CC([O-])C.CC([O-])C.CC([O-])C.[Ti+4]>[Si:1]([O:8][C:9]1[C:24]2[CH2:23][S:22][CH2:21][C@@H:20]([C:25]([O:27][CH2:28][CH3:42])=[O:26])[NH:19][C:18](=[O:29])[C@@H:17]([NH:30][C:31]([O:33][C:34]([CH3:35])([CH3:37])[CH3:36])=[O:32])[CH2:16][O:15][C:14](=[O:38])[C:13]=2[C:12]([CH3:39])=[C:11]([O:40][CH3:41])[CH:10]=1)([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:2])[CH3:3]

Participants

5

Reactant 2

HCID 702EthanolHCID 11215656HCID 11215656, compound

Product 1

HCID 54410145HCID 54410145, compound

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 61 mg of tert-butyl (4R, 7S)-14-(tert-butyldimethylsilyloxy)-1,3,4,5,6,7,8,10-octahydro-12-methoxy-4-methoxycarbonyl-11-methyl-6,10-dioxo-9,2,5-benzoxathiaazacyclododecine-7-carbamate and 11.4 mg of tetraisopropyl orthotitanate in 2 ml of ethanol was heated at reflux for 40 hours. The solution was diluted with ethyl acetate and washed successively with 1N hydrochloric acid and with brine. The organic layer was dried over sodium sulfate and evaporated in vacuo. The residue was chromatographed on silica gel using ethyl acetate/hexane (1:2, v/v) as eluent to yield tert-butyl (4R, 7S)-14-(tert-butyldimethylsilyloxy)-4-ethoxycarbonyl-1,3,4,5,6,7,8,10-octahydro-12-methoxy-11-methyl-6,10-dioxo-9,2,5-benzoxathiaazacyclododecine-7-carbamate. This material was treated with ammonium fluoride in methanol in an analogous manner to the procedure described in Example 13 to yield, after crystallization from ethyl acetate/hexane, tert-butyl (4R, 7S)-4-ethoxycarbonyl-1,3,4,5,6,7,8,10-octahydro-14-hydroxy-12-methoxy-11-methyl-6,10-dioxo-9,2,5-benzoxathiaazacyclododecine-7-carbamate as a white solid.

Workup

  1. temperatureat reflux for 40 hours
  2. washwashed successively with 1N hydrochloric acid and with brine
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. customevaporated in vacuo
  5. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-0efcfa507d62423e90f4b41654f06f4a
Source dataset
uspto-grants-1996_01
Patent number
US05486466

Reaction notes

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