Methanesulfonyl chloride → HCID 24801408, compound

HRID 2061337Notes

Reaction equation

HRID 2061337 reaction equation
[CH3:1][S:2](Cl)(=O)=O.O[CH2:7][CH:8]1[CH2:11][N:10]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:9]1.CCN(C(C)C)C(C)C.C[S-].[Na+].CS(OCC1CN(C(OC(C)(C)C)=O)C1)(=O)=O>C(Cl)Cl.CN(C=O)C.C1(C)C=CC=CC=1>[CH3:1][S:2][CH2:7][CH:8]1[CH2:11][N:10]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:9]1

Participants

9

Reactant 5

HCID 31297Methanesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 4378561Sodium methanethiolateHCID 10583745tert-Butyl 3-(hydroxymethyl)azetidine-1-carboxylateHCID 21959416Tert-butyl 3-((methanesulfonyloxy)methyl)azetidine-1-carboxylate

Product 1

HCID 24801408HCID 24801408, compoundYield 27%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

Methanesulfonyl chloride (0.53 mL, 6.8 mmol) was added dropwise to a stirred solution of 9 (530 mg, 2.8 mmol) and Hunig's base (0.986 mL, 5.6 mmol) in CH2Cl2 (10 mL) and left overnight at room temperature. The reaction was then diluted with CH2Cl2 (100 mL) and washed with water (25 mL), brine (25 mL), dried (MgSO4) and concentrated in vacuo. Sodium thiomethoxide (218 mg, 3109 μmol) was added portionwise to a solution of the residue, presumably tert-butyl 3-(methanesulfonyloxymethyl)azetidine-1-carboxylate (550 mg, 73%), in DMF (5 mL) and stirred at room temperature overnight. The reaction was diluted with toluene (100 mL) and washed with water (25 mL), brine (25 mL), dried (MgSO4) and concentrated in vacuo. Chromatography (MeOH/CH2Cl2=5:95) of the resulting residue afforded 13 as an oil (120 mg, 27%). 1H NMR (CDCl3): δ 3.98 (m, 2H), 3.54 (m, 2H), 2.65 (brs, 3H), 2.03 (s, 3H), 1.37 (s, 9H). 13C NMR (CDCl3): δ 155.3, 78.3, 53.1, 37.4, 27.4, 14.5.

Workup

  1. washwashed with water (25 mL), brine (25 mL)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. washwashed with water (25 mL), brine (25 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8bc86ee08cd0477a8ad24c55a945ffa3
Source dataset
uspto-grants-2012_10
Patent number
US08283345B2

Reaction notes

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