Abstract
The enantioselective synthesis of the tetrahydrofuran fragment of (-)-gymnodimine, a potent marine neurotoxin, has been achieved in 13% overall yield and 16 steps from 1,3-propanediol. Key features of the convergent synthesis include a chiral auxiliary-mediated, anti-aldol reaction and a substrate controlled allegation of a furanose. Model studies of an asymmetric, intermolecular Heck reaction were investigated as an approach to the chiral butenolide of gymnodimine. The feasibility of the Heck reaction between substituted enol tiflates and dihydrofuran derivatives was demonstrated. The applicability of the Peterson-like, cyclic imine synthesis has also been demonstrated in model studies. Alkyllithiums and N-silylated lactams underwent a Peterson-like reaction and resulted in a new carbon-carbon bond in addition to the desired cyclic imine functionality similar to that found in gymnodimine.
Yang, Ju (1999). Synthetic studies of the potent marine toxin, (-)-gymnodimine. Master's thesis, Texas A&M University. Available electronically from
https : / /hdl .handle .net /1969 .1 /ETD -TAMU -1999 -THESIS -Y2.