Triphenylphosphine → (S)-Tert-butyl 2-(((5-bromopyridin-3-YL)oxy)methyl)azetidine-1-carboxylate

HRID 1780327Notes

Reaction equation

HRID 1780327 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.[C:32]([N:39]1[CH2:42][CH2:41][C@H:40]1[CH2:43][OH:44])([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33].[Br:45][C:46]1[CH:47]=[C:48](O)[CH:49]=[N:50][CH:51]=1>C1COCC1>[Br:45][C:46]1[CH:47]=[C:48]([O:44][CH2:43][C@@H:40]2[CH2:41][CH2:42][N:39]2[C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[CH:49]=[N:50][CH:51]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5995293-Bromo-5-hydroxypyridineHCID 5462977Diethyl azodicarboxylateHCID 10511797tert-butyl (2S)-2-(hydroxymethyl)azetidine-1-carboxylate

Product 1

HCID 10688713(S)-Tert-butyl 2-(((5-bromopyridin-3-YL)oxy)methyl)azetidine-1-carboxylateYield 47.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Triphenylphosphine (4.01 g, 15.3 mmol) and DEAD (2.43 mL, 15.3 mmol) were dissolved in 30 mL of THF at 0° C., and the mixture was stirred for for 10 minutes. Samples of 1-BOC-2-(S)-azetidinemethanol (2.86 g, 15.3 mmol), prepared as described above, and 5-bromo-3-hydroxypyridine (1.505 g, 10.2 mmol) were added, and the reaction mixture was stirred for 40 hours at room temperature. The volatiles were removed under vacuum, and the residue was triturated with hexane. The hexane was removed, and the residue was chromatographed on a silica gel column, eluting with hexane:ether 10:1 to 10:2 to afford the title compound as a colorless oil (1.669 g). MS (CI/NH3) m/z 344 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ1.42 (s, 9H), 2.31 (m, 2H), 3.89 (m, 2H), 4.12 (m, 1H), 4.322 (m, 1H), 4.52 (m, 1H), 7.43 (m, 1H), 8.29 (m, 2H).

Workup

  1. additionwere added
  2. stirringthe reaction mixture was stirred for 40 hours at room temperature
  3. customThe volatiles were removed under vacuum
  4. customthe residue was triturated with hexane
  5. customThe hexane was removed
  6. customthe residue was chromatographed on a silica gel column
  7. washeluting with hexane:ether 10:1 to 10:2

Sources & evidence

ORD record
ord-4e23db322d1546b0b6d7faed64c40fde
Source dataset
uspto-grants-1997_05
Patent number
US05629325

Reaction notes

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