Total synthesis of epi-7-deoxypancratistatin via aza-Payne rearrangement and intramolecular cyclization.
[reaction: see text] epi-7-Deoxypancratistatin containing the cis-fused phenanthridone core was synthesized in 12 steps from bromobenzene. Key features of this synthesis include the enzymatic oxidation of bromobenzene with toluene dioxygenase, selective opening of a cyclic sulfate over an aziridine with oxygen nucleophiles, and an intramolecular Lewis acid-catalyzed cyclization onto an epoxy conduramine derived via aza-Payne rearrangement.
Rinner
Uwe
U
Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, USA.
Siengalewicz
Peter
P
Hudlicky
Tomas
T
D000470:Alkaloids / Q000138:chemical synthesis*; D047151:Amaryllidaceae Alkaloids; D000970:Antineoplastic Agents / Q000138:chemical synthesis*; D001372:Aza Compounds / Q000138:chemical synthesis; D003500:Cyclization; D007202:Indicators and Reagents; D007546:Isoquinolines / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D019684:Magnoliopsida
D000470:Alkaloids; D047151:Amaryllidaceae Alkaloids; D000970:Antineoplastic Agents; D001372:Aza Compounds; D007202:Indicators and Reagents; D007546:Isoquinolines; C446682:epi-7-deoxypancratistatin