Pyridine → (s)-1-t-Butyloxycarbonyl-2-toluensulfonyloxymethylazetidine

HRID 367055Notes

Reaction equation

HRID 367055 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH2:10][C@H:9]1[CH2:12][OH:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:14]1(C)[CH:19]=[CH:18][C:17]([S:20](Cl)(=[O:22])=[O:21])=[CH:16][CH:15]=1.N1C=CC=C[CH:26]=1>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH2:11][CH2:10][C@H:9]1[CH2:12][O:13][S:20]([C:17]1[C:18]([CH3:26])=[CH:19][CH:14]=[CH:15][CH:16]=1)(=[O:21])=[O:22])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 10511797tert-butyl (2S)-2-(hydroxymethyl)azetidine-1-carboxylate

Product 1

HCID 88183079(s)-1-t-Butyloxycarbonyl-2-toluensulfonyloxymethylazetidine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of (2S)-1-t-butyloxycarbonyl-2-azetidinemethanol (22.6 g, 0.121 mol) in 40 mL of pyridine was treated with p-toluenesulfonyl chloride (27.6 g, 0.145 mol). The resulting mixture was stirred at room temperature for 16 hours, diluted with CH2Cl2 and washed sequentially with 1 N aqueous HCl, H2O, saturated aqueous K2CO3, and brine. The organic phase was dried (Na2SO4) and concentrated. Purification by chromatography (silica gel; Hexane/EtOAc, 80:20) afforded 32.8 g of a white solid which was recrystallized from CH2Cl2 /hexane to afford the title compound as thin white needles: mp 59-60° C.; 1H NMR (CDCl3, 300 MHz) δ 1.37 (s, 9H), 2.15-3.28 (m, 2H), 2.44 (s, 3H), 3.74-3.81 (m, 2H), 4.13 (dd, J=3.1, 10.2 Hz, 1H), 4.23-4.34 (m, 2H), 7.35 (d, J=8.1 Hz, 2H), 7.80 (d, J=8.2 Hz, 2H); MS (CI/NH3) m/z: 242 (M+H)+.

Workup

  1. washwashed sequentially with 1 N aqueous HCl, H2O, saturated aqueous K2CO3, and brine
  2. dry with materialThe organic phase was dried (Na2SO4)
  3. concentrationconcentrated
  4. customPurification by chromatography (silica gel; Hexane/EtOAc, 80:20)

Sources & evidence

ORD record
ord-18a559f37fb64ac7973a5dc684228282
Source dataset
uspto-grants-2000_10
Patent number
US06133253

Reaction notes

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