Triphenylphosphine → HCID 54136796, compound

HRID 375768Notes

Reaction equation

HRID 375768 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]1[CH2:20][O:19][C:18](=[O:21])[C:17]2[C:22]([CH3:36])=[C:23]([O:34][CH3:35])[CH:24]=[C:25]([O:26][Si](C(C)(C)C)(C)C)[C:16]=2[CH2:15][S:14][CH2:13][C@@H:12]([C:37]([OH:39])=O)[NH:11][C:10]1=[O:40])=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:41]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:42]=1.C([Mg]Br)C.[F-].[NH4+]>O1CCCC1.C(OCC)(=O)C.CO.O>[OH:26][C:25]1[C:16]2[CH2:15][S:14][CH2:13][C@@H:12]([C:37](=[O:39])[CH2:41][CH3:42])[NH:11][C:10](=[O:40])[C@@H:9]([NH:8][C:6]([O:5][C:1]([CH3:3])([CH3:4])[CH3:2])=[O:7])[CH2:20][O:19][C:18](=[O:21])[C:17]=2[C:22]([CH3:36])=[C:23]([O:34][CH3:35])[CH:24]=1

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 25516Ammonium fluorideHCID 22858370HCID 22858370, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 54136796HCID 54136796, compoundYield 6.7%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 90 mg of (4R,7S)-7-tert-butoxycarbonylamino-14-tert-butyldimethylsilyloxy-1,3,4,5,6,7,8,10-octahydro-12-methoxy-11-methyl-6,10-dioxo-9,2,5-benzoxathiaazacyclododecine-4-carboxylic acid in 1.5 ml of tetrahydrofuran were added 49 mg of dipyridyl-2,2-disulfide and 79 mg of triphenylphosphine. The solution was stirred at 0° C. for 1 hour, and then 0.15 ml of a 1M solution of ethylmagnesium bromide in tetrahydrofuran were added. The mixture was stirred at 0° C. for 30 minutes, and then 0.5 ml of water were added, and stirring was continued for 5 minutes. The mixture was diluted with ethyl acetate and washed successively with 1N hydrochloric acid and with brine. The organic phase was dried over sodium sulfate, evaporated in vacuo, and the residual oil was chromatographed on silica gel using acetone/hexane (1:4, v/v) as eluent. The (tert-butyldimethylsilylated)-product obtained was treated with ammonium fluoride in methanol in an analogous manner to the procedure described in Example 13 to yield 5 mg of tert-butyl (4R, 7S)-1,3,4,5,6,7,8,10-octahydro- 14-hydroxy-12-methoxy-11-methyl-4-propionyl-6,10-dioxo-9,2,5-benzoxathiaazacyclododecine-7-carbamate as pale yellow foam.

Workup

  1. stirringThe mixture was stirred at 0° C. for 30 minutes
  2. stirringstirring
  3. waitwas continued for 5 minutes
  4. washwashed successively with 1N hydrochloric acid and with brine
  5. dry with materialThe organic phase was dried over sodium sulfate
  6. customevaporated in vacuo
  7. customthe residual oil was chromatographed on silica gel
  8. customThe (tert-butyldimethylsilylated)-product obtained

Sources & evidence

ORD record
ord-3d90f5c2d9c844828c95f7d5d4d9466f
Source dataset
uspto-grants-1996_01
Patent number
US05486466

Reaction notes

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