Oxygen → Methyl(2S)-2-(tert-butoxy)-2-[(22S)-17-fluoro-5-(2-hydroxypropan-2-yl)-4,22,28-trimethyl-21,27-dioxa-1,7,34-triazahexacyclo[26.2.2.16,9.110,14.02,7.015,20]tetratriaconta-2,4,6(34),8,10(33),11,13,15(20),16,18-decaen-3-yl]acetate

HRID 1482149Notes

Reaction equation

HRID 1482149 reaction equation
[C:1]([O:5][C@@H:6]([C:11]1[C:40]([CH3:41])=[C:39]([C:42]([CH3:44])=[CH2:43])[C:38]2=[N:45][C:35]3=[CH:36][N:37]2[C:12]=1[N:13]1[CH2:50][CH2:49][C:16]([CH3:51])([O:17][CH2:18][CH2:19][CH2:20][CH2:21][C@H:22]([CH3:48])[O:23][C:24]2[CH:25]=[CH:26][C:27]([F:47])=[CH:28][C:29]=2[C:30]2[CH:46]=[C:34]3[CH:33]=[CH:32][CH:31]=2)[CH2:15][CH2:14]1)[C:7]([O:9][CH3:10])=[O:8])([CH3:4])([CH3:3])[CH3:2].[BH4-].[Na+].[O:54]=O>C(O)C.[Fe+2]>[C:1]([O:5][C@@H:6]([C:11]1[C:40]([CH3:41])=[C:39]([C:42]([OH:54])([CH3:44])[CH3:43])[C:38]2=[N:45][C:35]3=[CH:36][N:37]2[C:12]=1[N:13]1[CH2:50][CH2:49][C:16]([CH3:51])([O:17][CH2:18][CH2:19][CH2:20][CH2:21][C@H:22]([CH3:48])[O:23][C:24]2[CH:25]=[CH:26][C:27]([F:47])=[CH:28][C:29]=2[C:30]2[CH:46]=[C:34]3[CH:33]=[CH:32][CH:31]=2)[CH2:15][CH2:14]1)[C:7]([O:9][CH3:10])=[O:8])([CH3:2])([CH3:3])[CH3:4]

Participants

6

Reactant 3

HCID 977OxygenHCID 4311764Sodium borohydride2×HCID 118316348Methyl(2S)-2-(tert-butoxy)-2-[(22S)-17-fluoro-4,22,28-trimethyl-5-(prop-1-en-2-yl)-21,27-dioxa-1,7,34-triazahexacyclo[26.2.2.16,9.110,14.02,7.015,20]tetratriaconta-2,4,6(34),8,10(33),11,13,15(20),16,18-decaen-3-yl]acetate

Product 1

HCID 118316385Methyl(2S)-2-(tert-butoxy)-2-[(22S)-17-fluoro-5-(2-hydroxypropan-2-yl)-4,22,28-trimethyl-21,27-dioxa-1,7,34-triazahexacyclo[26.2.2.16,9.110,14.02,7.015,20]tetratriaconta-2,4,6(34),8,10(33),11,13,15(20),16,18-decaen-3-yl]acetate

Reagents, catalysts & solvents 2

HCID 27284Ferrous cationCatalystHCID 702EthanolSolvent

Procedure

Methyl(2S)-2-(tert-butoxy)-2-[(22S)-17-fluoro-4,22,28-trimethyl-5-(prop-1-en-2-yl)-21,27-dioxa-1,7,34-triazahexacyclo[26.2.2.16,9.110,14.02,7.015,20]tetratriaconta-2,4,6(34),8,10(33),11,13,15(20),16,18-decaen-3-yl]acetate (50 mg, 0.072 mmol, 1 equiv) was dissolved in ethanol (0.86 mL). To this solution was added iron(II) phthalacyanine (4.07 mg, 7.16 μmol, 0.1 equiv) and sodium borohydride (5.42 mg, 0.143 mmol, 2 equiv). The reaction was stirred under air for 1 hour. No reaction. The mixture was then placed under oxygen balloon and stirred for 2 hours. To this solution was added 10 mg catalyst and 10 mg sodium borohydride and stirred under the oxygen balloon again. It was found that the vial emitted heat and the solution of the reaction turned to dark purple and back to blue again. The reaction was stirred overnight. The reaction completed 30% by LCMS. It was used as is for the next reaction. LCMS (ESI, M+1): 716.4.

Workup

  1. customNo reaction
  2. stirringstirred for 2 hours
  3. temperatureemitted heat
  4. stirringThe reaction was stirred overnight
  5. customas is for the next reaction

Sources & evidence

ORD record
ord-0d7a41d4eb474f9187af7b48edfea057
Source dataset
uspto-grants-2016_08
Patent number
US09409922B2

Reaction notes

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