Sodium Azide → t-butyl (1R)-2-azido-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate

HRID 1874625Notes

Reaction equation

HRID 1874625 reaction equation
Br[CH2:2][C@H:3]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH:12]([CH3:16])[CH2:13][CH2:14][CH3:15])=[CH:6][CH:5]=1.[N-:25]=[N+:26]=[N-:27].[Na+]>CN(C)C=O>[N:25]([CH2:2][C@H:3]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH:12]([CH3:16])[CH2:13][CH2:14][CH3:15])=[CH:6][CH:5]=1)=[N+:26]=[N-:27]

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 86658396t-butyl (1R)-2-bromo-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate

Product 1

HCID 86658397t-butyl (1R)-2-azido-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamateYield 88%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of t-butyl (1R)-2-bromo-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate (17.8 g, 44.5 mmol) in dimethylformamide was added sodium azide (11.56 g, 178 mmol) and the reaction mixture was stirred at room temperature for 1 h. The reaction was quenched by addition of water (25 mL) and the mixture was transferred to a separatory funnel and the aqueous layer was extracted with dichloromethane (3×40 mL). The combined organic layers were washed with brine (25 mL), dried over MgSO4, filtered and concentrated. The residue was purified by column chromatography on silica gel (30→40% ethyl acetate in hexanes) to afford t-butyl (1R)-2-azido-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate (14.2 g, 88% yield) as a yellow solid: 1H NMR (400 MHz, CDCl3) δ 7.19 (d, J=8.6 Hz, 2H), 6.86 (d, J=8.8 Hz, 2H), 5.01 (d, J=7.8 Hz, 1H), 4.78 (br. s., 1H), 3.78 (dd, J=9.1, 5.8 Hz, 1H), 3.68 (dd, J=8.8, 6.5 Hz, 1H), 3.57 (d, J=4.8 Hz, 2H), 1.86-1.97 (m, 1H), 1.42 (s, 9H), 1.26-1.51 (m, 3H), 1.14-1.24 (m, 1H), 0.99 (d, J=6.5 Hz, 3H), 0.90 (t, J=7.2 Hz, 3 H); LRMS (ESI) m/e 363.3 [(M+H)+, calcd for C19H31N4O3Br 363.2].

Workup

  1. customThe reaction was quenched by addition of water (25 mL)
  2. customthe mixture was transferred to a separatory funnel
  3. extractionthe aqueous layer was extracted with dichloromethane (3×40 mL)
  4. washThe combined organic layers were washed with brine (25 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography on silica gel (30→40% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-7eb5bd0fd00f4c1985ac2f1657791b08
Source dataset
uspto-grants-2012_11
Patent number
US08304577B2

Reaction notes

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