Attempts to mimic key bond-forming events associated with the proposed biogenesis of the pentacyclic lamellarins

The pyrrole-tethered veratroles 16 and 27 each engage in PIFA-induced oxidative cyclization reactions to give compounds 22 and 29, respectively, which incorporate a key tricyclic fragment associated with the title natural products. In contrast, the corresponding catechols 11 and 12 only produce polymeric materials on subjection to analogous reaction conditions. Efforts to study lactone ring formation by the oxidative cyclization of catechol 30 and veratrole 38 have been thwarted by an inability to prepare the former substrate and decomposition of the latter. The reported conversions 44 -> 45 and 46 -> 47 suggest that a C2-carboxy group attached to the pyrrole ring can 'direct' the oxidative cyclization of N-tethered aryl groups. The acquisition of compound 22 by the means described herein provides an adventitious and concise route to the racemic modification of the pyrrolo[2,1-a] isoquinoline alkaloid crispine A ( 52).