Oxidative carbocation formation in macrocycles: synthesis of the neopeltolide macrocycle.
Macrocyclic oxocarbenium ions can be formed from macrolactones that contain benzylic or allylic ether groups through oxidative carbon-hydrogen-bond activation mediated by 2,3-dichloro-4,5-dicyanoquinone (DDQ). The applicability of this efficient reaction to complex-molecule synthesis was demonstrated by its use in a brief formal synthesis of neopeltolide (see retrosynthetic scheme) to form the tetrahydropyrone ring.
Tu
Wangyang
W
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.
Floreancig
Paul E
PE
D003500:Cyclization; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction
D018942:Macrolides; C519136:neopeltolide