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A couple catalytic aziridine-forming reactions of α-imino esters have been reported but none employ aryldiazomethanes, see references 4h and 4x
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A couple catalytic aziridine-forming reactions of α-imino esters have been reported but none employ aryldiazomethanes, see references 4h and 4x.
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Phenyldiazomethane was synthesized according to literature procedure: Creary, X. Org. Synth. 1986, 64, 207.
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(a) Phenyldiazomethane was synthesized according to literature procedure: Creary, X. Org. Synth. 1986, 64, 207.
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18144398606
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Aryldiazomethanes are not commercially available and there have been several reports of explosions related to use of these substances. Encouraging developments have been recently reported for the in situ generation of aryldiazomethane compounds, see: Fulton, J. R, Aggarwal, V. K, de Vicente, J, Chem. 2005, 1479
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(b) Aryldiazomethanes are not commercially available and there have been several reports of explosions related to use of these substances. Encouraging developments have been recently reported for the in situ generation of aryldiazomethane compounds, see: Fulton, J. R.; Aggarwal, V. K.; de Vicente, J. Eur. J. Org. Chem. 2005, 1479.
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2O, 0.33 M 4 in toluene at -80°C). For polymerizations of 4, see: Bawn, C. E. H.; Ledwith, A.; Matthies, P. J. Polym. Sci. 1958, 33, 21.
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2O, 0.33 M 4 in toluene at -80°C). For polymerizations of 4, see: Bawn, C. E. H.; Ledwith, A.; Matthies, P. J. Polym. Sci. 1958, 33, 21.
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The protic acid, TfOH, was recently found to be an effective catalyst for aziridine formation of imines with diazo acetates, see reference 4h.
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The protic acid, TfOH, was recently found to be an effective catalyst for aziridine formation of imines with diazo acetates, see reference 4h.
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3 use 10 mol%, presumably due to no optimization, see references: 4e, 4l, 4r, 4w, 4x, 4z, and 5c.
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3 use 10 mol%, presumably due to no optimization, see references: 4e, 4l, 4r, 4w, 4x, 4z, and 5c.
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The only other report of a highly active Lewis acid catalyst in the synthesis of aziridines from imines with any diazo compound involves use of SnCl4 0.05 mol% for 50% conversion in 50 min, see reference 5a
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4 (0.05 mol% for 50% conversion in 50 min), see reference 5a.
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In these cases, an insufficient level of Lewis acid is present to selectively decompose the trans-aziridine isomer, as has been reported in reference 4m
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In these cases, an insufficient level of Lewis acid is present to selectively decompose the trans-aziridine isomer, as has been reported in reference 4m.
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Bravo, P.; Capelli, S.; Crucianelli, M.; Guidetti, M.; Markovsky, A. L.; Meille, S. V.; Soloshonok, V. A.; Sorochinsky, A. E.; Viani, F.; Zanda, M. Tetrahedron 1999, 55, 3025.
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Typical Synthetic Procedure: To a CH2Cl2 solution (5 mL) of imine 3 (216 mg, 1.04 mmol) at -78°C was added BF3·Et2O (5 mol, 6.5 μL, 52 μmol) and the solution was stirred at -78°C for 15 min. To this pale yellow solution was added, all at once, 4 (1.1 equiv, 327 μL of 3.5 M 4 in CH 2Cl2) and stirring was continued for 1.5 h at -78°C. The reaction flask was then removed from the -78°C bath and stirring was continued for another 45 min during which time the reaction mixture came to r.t. The reaction mixture was diluted with CH2Cl2 (5 mL, washed with a sat. aq solution of NaHCO3 (3 x 10 mL, dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to provide a yellow oil that was purified on silica gel by flash column chromatography using PE-EtOAc (from 95:5 to 85:15) to provide pure cis
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5f (269.7 mg, 87%) as an off-white solid.
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