Structural characterization of an enantiomerically pure amino acid imidazolide and direct formation of the beta-lactam nucleus from an alpha-amino acid.

Decomposition of a diazo beta-ketoamide derived from N-trityl serine imidazolide and N-protected acetanilides provides, instead of the expected 3-acyloxindole product, an enantiomerically pure (EP) beta-lactam. The amino acid stereocenter is incorporated, the second chiral center is induced, and trityl protection of the beta-lactam ring is realized for the first time. The desired 3-acyloxindole is obtained from oxindole and Tr-Ser(OBn)-imidazole, the X-ray of which provides the first structural determination of an EP amino acid imidazolide.

From dimerization, to cycloaddition, to atom transfer cyclization: the further chemistry of TMM diradicals.

We describe [a] the first examples of intramolecular cycloaddition of a TMM diyl to a remotely tethered aldehyde, [b] the effect of a Lewis acid upon the course of TMM chemistry, [c] examples of exclusive intramolecular cycloaddition, competitive cycloaddition and ATC, and exclusive ATC, and [d] a set of predictive guidelines with which to assess whether cycloaddition or ATC will be the preferred path, and when the two processes will be competitive. Remarkably, a wide variety of structures can be obtained simply by varying the length of the tether within the diazenes investigated. DFT calculations were used to probe the energy surfaces for both atom transfer and cycloaddition.