Total synthesis of +/--hyphodermins A and D.

Wendy A Loughlin, Ian D Jenkins, Luke C Henderson, Marc R Campitelli, Peter C Healy

School of Biomolecular and Physical Sciences, Griffith University, Brisbane, QLD, 4111, Australia. w.loughlin@griffith.edu.au

The Journal of organic chemistry 2008 May 2

filter terms:

An efficient formal synthesis of (+/-)-hyphodermins A and D, metabolites of Hyphoderma radula, has been completed in 12 and 11 steps, respectively. The tricyclic carbon skeleton of enone 6 was rapidly assembled from diester 11 via an alpha brominationn-elimination sequence followed by anhydride formation. Regioselective reduction of the lactone group of enone 6 with LiAlH(t-BuO) 3 gave lactol 15. Lactol 15 was converted in two steps to (+/-)-hyphodermin D, without the need for complex protection-deprotection strategies. Lactol 15 was converted in three steps to (+/-)-hyphodermin A, via the key step of epoxidation of an enone in the presence of a THP lactol. A combination of NMR and ab initio studies suggests that the structures of hyphodermin C and D should be interchanged.

Citation

Wendy A Loughlin, Ian D Jenkins, Luke C Henderson, Marc R Campitelli, Peter C Healy. Total synthesis of +/--hyphodermins A and D. The Journal of organic chemistry. 2008 May 2;73(9):3435-40