Chiral Aziridines—Their Synthesis and Use in Stereoselective Transformations

Abstract

The preparation of enantiomerically pure compounds is one of the major areas of organic chemistry. Much emphasis is placed on the elaboration of naturally occurring starting materials and on the development of techniques for enantio‐selective transformations of achiral substrates. In this field, chiral aziridines form an attractive class of compounds, since they are available in enantiomerically pure (or highly enriched) form by a variety of procedures and can be used for asymmetric synthesis in a number of different ways. The chemistry of aziridines is dominated by ring‐opening reactions, the driving force for which is relief of ring strain. By suitable choice of sub‐stituents on the carbon and nitrogen atoms, excellent stereo‐ and regiocontrol can be attained in ring‐opening reactions with a wide variety of nucleophiles, including organometallic reagents; this makes chiral aziridines useful as substrates for the synthesis of important biologically active species including alkaloids, amino acids, and /Mactam antibiotics. Substrate‐controlled diastereo‐selective synthesis is also possible by use of aziridines as removable chiral auxiliaries, while metalation at a ring carbon atom allows aziridines to be used as chiral reagents for asymmetric synthesis. Chiral bisaziridines can act as ligands for transition metals, and applications in the challenging field of enantioselective catalysis can be envisioned. Today, the exclusion of three‐membered carbo‐ and heterocycles from the arsenal of the organic chemist is inconceivable.H. Heimgartner, Angew. Chem. 1991, 103, 271; Angew. Chem. Int. Ed. Engl. 1991, 30, 238.