Synthesis gymnodimine

A hydrotelluration reaction, followed by a tellurium-lithium exchange, was used in the first step of the total synthesis of Gymnodimine 182 (Scheme 100).257... 

Several studies have been carried out for the synthesis of gymnodimine-components (Ahn et al. 2001 White et al. 2003 Johannes et al. 2005 Kong et al. 2005), but the total synthesis has yet to be achieved. The synthesis and production of intermediate components of gynmodimine appears essential for providing inummogens that will help its toxic monitoring in shellfish by methods other than the mouse bioassay. 

Kong, K., Moussa, Z. and Romo, D., 2005. Studies toward a marine toxin immunogen enantioselective synthesis of the spiro-cyclic imine of (-)-gymnodimine. Org Lett 7, 5127-5130. 

White, J.D., Wang, G. and Quaranta, L., 2003. Studies on the synthesis of gymnodimine. Stereocontrolled construction ofthe tetrahydrofuran subunit. Org Lett 5, 4109-4112. 

Romo and coworkers have utilized an enantioselective Cu(II)-catalyzed Diels-Alder cycloaddition to set the key all-carbon quaternary stereocenter in the spiro-cyclic imine core of the marine toxin immunogen (—)-Gymnodimine (251) [76]. Cu(SbF6)2/t-Bu-BOX (13)-catalyzed cycloaddition of diene (248) to a-methylene lactam (247) provides spirolactam (249) in high yield with high stereoselectivity (Scheme 17.55). Subsequent synthetic efforts resulted in an efficient synthesis of the spirocyclic imine portion of (251). 

Ahn, Y, Cardenas, G.I., Yang, J., and Romo, D. (2001) Studies toward gymnodimine Development of a single-pot Hua reaction for the synthesis of highly hindered cyclic imines. Org. Lett., 3, 751-754. 

Trzoss, M. and Brimble, M.A. (2003) Synthesis of spirocyclic imines Key pharmacophores in the shellfish toxins spirolides and gymnodimine. Synlett, 2042-2046. 

Kong, K Romo, D and Lee, C. (2009) Enantioselective total synthesis of Ihe marine toxin (-)-gymnodimine employing a Barbier-type macrocydization. Angew. Chem. Int Ed., 48, 7402-7405. 

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