Versatile New Reagent for Nitrosation under Mild Conditions
Jordan D. Galloway, Cristian Sarabia, James C. Fettinger, Hrant P. Hratchian and Ryan D. Baxter*
*Department of Chemistry and Chemical Biology, University of California, Merced, Merced, California 95343, United States,
Email: rbaxter
ucmerced.edu
J. D. Galloway, C. Sarabia, J. C. Fettinger, H. P. Hratchian, R. D. Baxter, Org. Lett., 2021, 23, 3253-3258.
DOI: 10.1021/acs.orglett.1c00637
see article for more reactions
Abstract
3,3-Dimethyl-2-nitroso-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide can be used as chemical reagent for transnitrosation under mild experimental conditions. This reagent is stable to air and moisture across a broad range of temperatures and offers high functional group tolerance for substrates that are susceptible to oxidation or reversible transnitrosation. The sulfonamide byproduct is easily recovered to regenerate the reagent.
see article for more examples
General Procedure for Nitrosation
The threads of a 3 mL borosilicate scintillation vial were thoroughly taped with Teflon tape. To this vial containing a stir bar was added substrate (0.2 mmol, 1 equiv), and 3,3-dimethyl-2-nitroso-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide (54.0 mg, 0.24 mmol, 1.2 equiv). Dichloromethane (2 mL) was then added and the reaction was stirred at room temperature on a stir plate until completed (thinlayer chromatography). In some reactions when heating is required (80 °C) the vials are stired on a hotplate and dichloroethane (2 mL) or acetonitrile (2 mL) was used in replacement of dichloromethane. Upon completion, the solvent was removed under reduced pressure, crude mixture was directly absorbed onto silica and purified by silica gel chromatography to yield the desired product.
General Procedure for Acid Catalyzed Nitrosation
The threads of a 3 mL borosilicate scintillation vial were thoroughly taped with Teflon tape. To this vial containing a stir bar was added substrate (0.2 mmol, 1 equiv), and 3,3-dimethyl-2-nitroso-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide (54.0 mg, 0.24 mmol, 1.2 equiv). Acetonitrile (2 mL) and trifluoracetic acid (3.1 µL, 20 mol %) was then added and the reaction was stirred at room temperature until completed (thin-layer chromatography). Upon completion, the solvent was removed under reduced pressure, crude mixture was directly absorbed onto silica and purified by silica gel chromatography to yield the desired product.
Key Words
nitrosamines, O-nitroso compounds
ID: J54-Y2021
