title: Total synthesis of (-)-rhazinilam: asymmetric C[bond]H bond activation via the use of a chiral auxiliary.
abstract: 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.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: James A
authors.initials: JA
authors.lastname: Johnson
authors.forename: Ning
authors.initials: N
authors.lastname: Li
authors.forename: Dalibor
authors.initials: D
authors.lastname: Sames
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis*; D000970:Antineoplastic Agents / Q000138:chemical synthesis*; D007212:Indolizines; D007769:Lactams; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D000970:Antineoplastic Agents; D007212:Indolizines; D007769:Lactams; D011758:Pyrroles; C009170:rhazinilam