UC Irvine

Chapter 1 focuses on the use of C–H activation in total synthesis and the strategies that these methods enable. Following a review of recent total syntheses using C–H activation to form a variety of rings, we discuss our efforts towards two total syntheses using C–H activation methodology. In this instance, desymmetrizing olefin hydroacylation offers a method to generate quaternary stereocenters on cyclic ketones in a rapid manner with high atom economy. The resulting cyclic scaffolds were used to develop a formal synthesis of the natural product (+)- tanikolide, a cyanotoxin from lyngbya majuscula, and in efforts towards the total synthesis of (– )-adalinine, an alkaloid natural product isolated from adalia bipunctata and adalia decempunctata.

Chapter 2 describes recent efforts to use aldehyde C–H activation in a tandem oxidation- dehydroformylation reaction that we have worked to develop. This new methodology offers the ability to directly transform primary alcohols directly to olefins while cleaving a carbon-carbon bond, a previously undocumented transformation.