Water → HCID 67148555, compound

HRID 2427473Notes

Reaction equation

HRID 2427473 reaction equation
C([O:3][C:4]([C:6]1([CH2:30][C:31]#[N:32])[CH2:11][CH2:10][CH:9]([O:12][Si:13]([C:26]([CH3:29])([CH3:28])[CH3:27])([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH2:8][CH2:7]1)=O)C.O.[BH4-].[Na+].[OH-].[NH4+]>C1COCC1.O.O.O.O.O.O.[Co](Cl)Cl>[C:26]([Si:13]([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[O:12][CH:9]1[CH2:10][CH2:11][C:6]2([C:4](=[O:3])[NH:32][CH2:31][CH2:30]2)[CH2:7][CH2:8]1)([CH3:29])([CH3:28])[CH3:27]

Participants

7

Reactant 4

HCID 962WaterHCID 14923Ammonium HydroxideHCID 4311764Sodium borohydrideHCID 67148556HCID 67148556, compound

Product 1

HCID 67148555HCID 67148555, compoundYield 18.5%

Reagents, catalysts & solvents 2

HCID 517166Dichlorocobalt hexahydrateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Treat a 0° C. mixture of 4-(tert-butyl-diphenyl-silanyloxy)-1-cyanomethyl-cyclohexanecarboxylic acid ethyl ester (7.19 g, 15.9 mmol), cobalt (II) chloride hexahydrate (1.90 g, 7.98 mmol) in THF (130 mL), and water (65 mL) portion-wise with sodium borohydride (3.02 g, 7.98 mmol). Warm to room temperature and stir for 16 hours under N2. Heat the reaction to 50° C. for 8 hours, cool to room temperature and stir 16 hours under N2. Treat the reaction with 28% ammonium hydroxide (2 mL) and filter through hyflo. Remove the solvent from the filtrate in vacuo and dilute the residue with minimal water and brine and extract three times with 3:1 chloroform:isopropanol. Dry the organic layer with Na2SO4 and remove the solvent in vacuo to afford crude product. Purify with a 0 to 10% methanol in CH2Cl2 gradient on silica gel to afford 1.20 g (18%) of the titled product. Rf=0.48 and 0.61 (9/1 CH2Cl2/methanol). MS (m/z): 408 (M+).

Workup

  1. additionTreat a 0° C.
  2. temperatureHeat
  3. customthe reaction to 50° C. for 8 hours
  4. temperaturecool to room temperature
  5. stirringstir 16 hours under N2
  6. additionTreat
  7. filtrationfilter through hyflo
  8. customRemove the solvent from the filtrate in vacuo
  9. additiondilute the residue with minimal water and brine
  10. extractionextract three times with 3:1 chloroform
  11. dry with materialDry the organic layer with Na2SO4
  12. customremove the solvent in vacuo
  13. customto afford crude product
  14. customPurify with a 0 to 10% methanol in CH2Cl2 gradient on silica gel

Sources & evidence

ORD record
ord-b07196c53db94a1dbffe91a448afccf5
Source dataset
uspto-grants-2011_06
Patent number
US07968585B2

Reaction notes

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