Total synthesis of (-)-rhazinilam: Asymmetric C-H bond activation via the use of a chiral auxiliary

The antitumor agent (-)-rhazinilam was synthesized in three major steps, namely the pyrrole synthesis, selective C-H bond activation, and direct macrolactam formation. The key step involved asymmetric C-H bond functionalization (dehydrogenation) of the diethyl group segment in intermediate 6. This was achieved by the attachment of chiral platinum complexes to the proximal nitrogen atom. A high degree of selectivity (60-75% ee) was achieved via the use of oxazolinyl ketone chiral auxiliaries.