Total synthesis and absolute configuration of the natural amino acid tetrahydrolathyrine.

The natural product tetrahydrolathyrine has been synthesized through an iminoiodane-mediated aziridination of a (2S)-allylglycinol derivative, which provided a 2:3 mixture of diastereoisomers. One of these diastereoisomers was converted to the natural product and the other to its C-4 epimer. The C-4 configuration was established from NOESY NMR analysis and X-ray structure of compounds derived from the non-natural diastereoisomer. Thus, tetrahydrolathyrine was shown to have the (2S,4R) absolute configuration.

Intramolecular PhI=O mediated copper-catalyzed aziridination of unsaturated sulfamates: a new direct access to polysubstituted amines from simple homoallylic alcohols.

[reaction: see text] Olefinic sulfamates derived from primary and secondary alcohols undergo intramolecular copper-catalyzed aziridination in the presence of iodosylbenzene to afford novel bicyclic fused aziridines. The latter were opened by various nucleophiles to give the corresponding substituted cyclic sulfamates, which in turn reacted, after nitrogen activation, with a second nucleophile at the carbon atom bearing the oxygen atom. Concomitant removal of the sulfonyloxy moiety thus gave access to polysubstituted amines.

Copper-catalyzed iminoiodane-mediated aminolactonization of olefins: application to the synthesis of 5,5-disubstituted butyrolactones.

A copper(I)-catalyzed reaction of a variety of 4-aryl-pent-4-enoates with nosyliminoiodane generated in situ provides the corresponding 5-aryl-5-nosylamidomethylbutyrolactones. The reaction presumably proceeds via an aziridine intermediate, which could be isolated in one case.