Dimethyl Sulfate → (1S*,2R*,4R*)-[4-azido-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexyl]-methyl-carbamic acid tert-butyl ester

HRID 7680Notes

Reaction equation

HRID 7680 reaction equation
[C:1]([O:5][C:6](=[O:29])[NH:7][C@H:8]1[CH2:13][CH2:12][C@@H:11]([N:14]=[N+:15]=[N-:16])[CH2:10][C@H:9]1[CH2:17][S:18]([C:21]1[CH:26]=[CH:25][C:24]([S:27][CH3:28])=[CH:23][CH:22]=1)(=[O:20])=[O:19])([CH3:4])([CH3:3])[CH3:2].[CH3:30][Si]([N-][Si](C)(C)C)(C)C.[K+].COS(OC)(=O)=O>C1COCC1>[C:1]([O:5][C:6](=[O:29])[N:7]([C@H:8]1[CH2:13][CH2:12][C@@H:11]([N:14]=[N+:15]=[N-:16])[CH2:10][C@H:9]1[CH2:17][S:18]([C:21]1[CH:22]=[CH:23][C:24]([S:27][CH3:28])=[CH:25][CH:26]=1)(=[O:19])=[O:20])[CH3:30])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 6497Dimethyl SulfateHCID 3251421Potassium bis(trimethylsilyl)amideHCID 86590249(1S*,2R*,4R*)-[4-Azido-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexyl]-carbamic acid tert-butyl ester

Product 1

HCID 86590250(1S*,2R*,4R*)-[4-azido-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexyl]-methyl-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

±(1S*,2R*,4R*)-[4-Azido-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexyl]-carbamic acid tert-butyl ester, from Example (55d) (389 mg) was dissolved in THF (3 ml) and cooled to −78° C. prior to the slow addition of a solution of 0.5M KHMDS in THF (2.65 ml). After 20 min, Me2SO4 (0.15 ml) was added. The reaction was warmed to rt and stirred for 2 h before the solution was quenched with sat. NH4Cl. This was extracted twice with EtOAc. The combined organic layer was dried, filtered, and concentrated. Flash chromatography of the resulting residue gave ±(1S*,2R*,4R*)-[4-azido-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexyl]-methyl-carbamic acid tert-butyl ester (207 mg): 1H NMR (CDCl3, δppm, 300 mHz) 1.39 (s, 9H), 1.55-1.93 (m, 4H), 2.00 (m, 1H), 2.52 (s, 3H), 2.65 (m, 1H), 2.80 (s, 3H), 3.00 (m, 2H), 3.81 (m, 3H), 7.34 (d, 2H), 7.80 (d, 2H).

Workup

  1. temperatureThe reaction was warmed to rt
  2. customwas quenched with sat. NH4Cl
  3. extractionThis was extracted twice with EtOAc
  4. customThe combined organic layer was dried
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-fbcb93dc67a145c3a7c4aba9eb8ad6dc
Source dataset
uspto-grants-2006_08
Patent number
US07087604B2

Reaction notes

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