(Diethylamino)sulfur trifluoride → Tert-butyl 1-fluoromethylcyclopropylsulfonylcarbamate

HRID 1481643Notes

Reaction equation

HRID 1481643 reaction equation
O[CH2:2][C:3]1([S:6]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])(=[O:8])=[O:7])[CH2:5][CH2:4]1.C(N(S(F)(F)[F:23])CC)C>C(Cl)Cl>[C:12]([O:11][C:10](=[O:16])[NH:9][S:6]([C:3]1([CH2:2][F:23])[CH2:5][CH2:4]1)(=[O:8])=[O:7])([CH3:15])([CH3:14])[CH3:13]

Participants

4

Reactant 2

HCID 123472(Diethylamino)sulfur trifluorideHCID 57816716HCID 57816716, compound

Product 1

HCID 70978761Tert-butyl 1-fluoromethylcyclopropylsulfonylcarbamateYield 72.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of tert-butyl 1-hydroxymethylcyclopropylsulfonylcarbamate (26.0 g, 103 mmol) in DCM (300 mL) was cooled to −78° C. To this solution was added diethylaminosulfur trifluoride (“DAST”, 41.0 mL, 310 mmol). The reaction mass was stirred at the same temperature for 30 min. The reaction mass was quenched with aqueous 1N NaOH solution. The organic layer was discarded and the aqueous layer was acidified to pH˜2 by using aq. 1.5 N HCl solution. The aqueous solution was extracted with DCM (50 mL×4). The combined organic layers were dried over anhydrous sodium sulfate; filtered; then concentrated to afford desired tert-butyl(1-(fluoromethyl)cyclopropyl)sulfonylcarbamate (19 g, 72%) as gummy solid. 1H NMR (400 MHz, DMSO-d6): δ ppm 11.25 (sb, 1H), 4.75 (s, 1H), 4.63 (s, 1H), 1.44 (s, 9H), 1.28 (m, 2H), 1.07 (m, 2H). 19F NMR: −211.7 (1F).

Workup

  1. customThe reaction mass was quenched with aqueous 1N NaOH solution
  2. extractionThe aqueous solution was extracted with DCM (50 mL×4)
  3. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationthen concentrated

Sources & evidence

ORD record
ord-0ad406a537c34faf87a03ec0ae61f668
Source dataset
uspto-grants-2016_08
Patent number
US09409943B2

Reaction notes

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