Marine natural products have long served as leading compounds for new therapeutic agents; however, their utilization is often extremely limited due to poor availability from their natural sources. Therefore, exploration of new synthetic techniques offers shortcuts in the production of such agents and the opportunity to improve the current state of the art. Studies directed toward the synthesis of these biologically active marine natural products inspire the development of new, efficient, economical, and environmentally friendly methods that are broadly useful for the synthesis of new pharmaceuticals and organic compounds for medicinal research.

The development of a wide range of new and exciting chemical transformations revolving around the rich chemistry of enolates is described. Specifically these studies include: 1) a stereoselective enolization of alpha-branched esters, 2) a diastereoselective Ireland-Claisen rearrangement, 3) the stereoselective formation of quaternary stereocenters, and 4) an asymmetric alkylation.

Additionally, the total synthesis of the marine natural products (+)-pinnatoxin A and (+)-pinnatoxin G will be discussed in detail. The diastereoselective Ireland-Claisen rearrangement is a featured method for the stereoselective installation of the quaternary stereocenter in the pinnatoxins and other related spiroimine natural products.