Sodium borohydride → HCID 71116109, compound

HRID 1423841Notes

Reaction equation

HRID 1423841 reaction equation
[N:1]([CH2:4][C:5]1([CH3:21])[CH2:20][CH2:19][CH2:18][C:7]2([O:11][C:10](=[O:12])[N:9]([CH2:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:8]2)[CH2:6]1)=[N+]=[N-].[BH4-].[Na+]>CO.O.O.O.O.O.O.[Ni](Cl)Cl>[NH2:1][CH2:4][C:5]1([CH3:21])[CH2:20][CH2:19][CH2:18][C:7]2([O:11][C:10](=[O:12])[N:9]([CH2:13][C:14]([CH3:16])([CH3:17])[CH3:15])[CH2:8]2)[CH2:6]1

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 71116099HCID 71116099, compound

Product 1

HCID 71116109HCID 71116109, compoundYield 94.8%

Reagents, catalysts & solvents 2

HCID 11791229Dichloronickel;hexahydrateCatalystHCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

To a light green 0° C. solution of 7-(azidomethyl)-7-methyl-3-neopentyl-1-oxa-3-azaspiro[4.5]decan-2-one (10.0 g, 34.0 mmol) and nickel (II) chloride hexahydrate (8.07 g, 34.0 mmol) in MeOH (226 mL) was added sodium borohydride (1.93 g, 51.0 mmol) in six portions. The reaction quickly became black and was allowed to stir at 0° C. for 3 h. The reaction mixture was concentrated and partitioned between 1 N NaOH (350 mL) and EtOAc (350 mL). The biphasic mixture was filtered through celite, and the layers were separated. The aqueous layer was extracted with EtOAc (2×150 mL). The combined organics were dried over MgSO4, filtered, and concentrated to afford the title compound (8.65 g, 90% crude yield) as a light yellow solid. 1H NMR (400 MHz, CDCl3) δ 3.33 (dd, J=8.53, 13.80 Hz, 2H), 3.06 (d, J=14.05 Hz, 1H), 2.93 (d, J=14.05 Hz, 1H), 2.43 (s, 2H), 1.99 (dt, J=1.76, 13.55 Hz, 1H), 1.89 (dt, J=3.48, 13.87 Hz, 1H), 1.69 (d, J=14.05 Hz, 1H), 1.57 (dt, J=4.11, 13.87 Hz, 1H), 1.29-1.47 (m, 3H), 1.15-1.28 (m, 1H), 1.08 (s, 3H), 0.96 (s, 9H).

Workup

  1. customThe reaction quickly became black
  2. concentrationThe reaction mixture was concentrated
  3. custompartitioned between 1 N NaOH (350 mL) and EtOAc (350 mL)
  4. filtrationThe biphasic mixture was filtered through celite
  5. customthe layers were separated
  6. extractionThe aqueous layer was extracted with EtOAc (2×150 mL)
  7. dry with materialThe combined organics were dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-2473b4b2f8c945429703d353ae5f481d
Source dataset
uspto-grants-2015_01
Patent number
US08927585B2

Reaction notes

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