Total synthesis of (-)-rhazinilam: asymmetric C[bond]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[bond]H bond activation, and direct macrolactam formation. The key step involved asymmetric C[bond]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.
Johnson
James A
JA
Department of Chemistry, Columbia University, New York, New York 10027, USA.
Li
Ning
N
Sames
Dalibor
D
D000470:Alkaloids / Q000138:chemical synthesis*; D000970:Antineoplastic Agents / Q000138:chemical synthesis*; D007212:Indolizines; D007769:Lactams; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
D000470:Alkaloids; D000970:Antineoplastic Agents; D007212:Indolizines; D007769:Lactams; D011758:Pyrroles; C009170:rhazinilam