| The work presented here is divided into three distinct projects. The first project (Chapter 2) pertains to the development of a new chemical reagent called potassium hydride in paraffin, KH(P). The remaining two projects (Chapters 3 & 4) pertain to the total synthesis of natural products.;Potassium hydride (KH) has long been known as a strong Bronsted base used in organic synthesis but has not been as widely applied as other bases. This is primarily due to the difficulty associated with handling and dispensing it accurately. I have discovered that KH as a 1:1 w/w homogenate in paraffin wax [KH(P)] solves these problems. This new reagent is an air stable solid at room temperature, allowing it to be accurately measured gravimetrically.;The second project describes the first total synthesis of the sesquiterpene natural product (--)-cameroonan-7alpha-ol (Chapter 3). Central to the synthesis of (--)-cameroonan-7alpha-ol was the specific conversion of C-H to C-C bonds. A novel combination of Rh(II)-mediated C-H functionalization followed immediately by Mn(III)-mediated oxidative radical cyclization was developed for the synthesis of [3.3.0] bicycles from acyclic starting material.;The final chapter describes my synthetic progress towards the total synthesis of the natural product ritterazine N (Chapter 4). The synthesis of a key tricyclic alpha-sulfonyl ketone subunit is described. Also, using a model compound, I have determined the diastereoselectivity of a key Sm(II)-mediated spirocyclization step. |
