Synlett 2007(13): 2025-2028  
DOI: 10.1055/s-2007-984872
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Catalytic Synthesis of Aziridines without the Usual Byproducts

Arindam Mazumdar, Zheng Xue, Michael F. Mayer*
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061, USA
Fax: +1(806)7421289; e-Mail: mf.mayer@ttu.edu;
Further Information

Publication History

Received 9 March 2007
Publication Date:
27 June 2007 (online)

Abstract

Complementary to existing routes, the Lewis acid catalyzed reactions of phenyldiazomethane with α-imino esters selectively produce cis-aziridine-2-carboxylates without competitive formation of enamino ester or carbene dimer byproducts.

    References and Notes

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9

A couple catalytic aziridine-forming reactions of α-imino esters have been reported but none employ aryldiazo-methanes, see references 4h and 4x.

13

The protic acid, TfOH, was recently found to be an effective catalyst for aziridine formation of imines with diazo acetates, see reference 4h.

14

Other reported catalytic aziridine syntheses that employ Yb(OTf)3 use 10 mol%, presumably due to no optimization, see references: 4e, 4l, 4r, 4w, 4x, 4z, and 5c.

15

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.

16

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.

18

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 CH2Cl2) and stirring was continued for 1.5 h at -78 °C. The reaction flask was then removed from the -78 ºC 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 × 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-5 [5f] (269.7 mg, 87%) as an off-white solid.