Aziridines carbon-based nucleophiles

Carbon-based nucleophiles continue to be examined in ring-opening reactions of aziridines. Select examples from the year 2014 include employment of indole derivatives in Friedel-Crafts-type reactions (14T4512, 14MI16478), utilization of malonate-type nucleophiles (14JA9190, 14EJ0767), and arylation reactions involving the use of N-heterocyclic... 

Similar to the epoxides, the most frequently encountered synthetic transformation for aziridines is nucleophilic ring-opening, whereby carbon- and heteroatom-based nucleophiles are comparably important. As an example of the former type, aziridine-2-carboxylates 100 can be ring-opened with higher order cuprates to give the protected amino acid derivatives 101, corresponding to attack at the less-substituted aziridine carbon [95TL151],... 

There is, of course, no paucity of examples using heteroatom-based nucleophiles. For example, aziridine-2-/-butyl carboxylate 102 reacts with primary amines to give the dialkylated diamino-propionic acid derivatives 103, which are interesting precursors for the synthesis of cyclosporin analogs. Again, attack occurs overwhelmingly at the B-carbon [95TL4955]. 

Hydroxymethylaziridine 67 undergoes ring opening in the presence of either carbon- or heteroatom-based nucleophiles upon treatment with 2 equiv of potassium hydride to provide the t)7aminoalcohol derivative 69. The key step of the reaction is considered to be an aza-Payne rearrangement of the deprotonated aziridine methanol to the... 

Based on this result, it has been proposed that the zwitterionic moiety IPr-C02 on MCM-41 may attack one of the carbon atoms of the aziridine ring to generate a new zwitterion (Scheme 4.36). Nucleophilic attack of the formed nitrogen anion to the carbon atom of the carbonyl group produced oxazoUdinones by intramolecular cyclic elimination. Finally, the MCM-41-IPr produced reacted quickly with CO2 to regenerate the MCM-41-IPr-C02 adduct. 

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