Rhodium(I)-Catalyzed [(3+2+2)] Carbocyclization Reactions of ACPs in Total Synthesis: Towards the Preparation of Tremulane Sesquiterpene Natural Products

Abstract

This thesis is divided into two main chapters. Chapter 1 focuses on transition metal-catalyzed higher-order carbocyclization reaction whilst Chapter 2 focuses on the total synthesis of tremulane sesquiterpene natural products. Chapter one of this thesis describes the optimization and development of the diastereoselective rhodium-catalyzed intramolecular [(3+2+2)] carbocyclization reaction of dieneyne alkylidenecyclopropanes. The chapter commences with an introduction to transition metal-catalyzed higher-order carbocyclization reactions, with a strong focus on [3+2+2] carbocyclization reactions. Section 1.2 describes our development of the diastereoselective rhodium-catalyzed intramolecular [(3+2+2)] carbocyclization reaction. This section highlights the optimal reaction conditions, scope, and generality of our methodology. Chapter two of this thesis focuses on the total synthesis of three tremulane sesquiterpene natural products. This section begins with an introduction to the tremulane family of natural products, followed by a summary of previous syntheses of two natural products. Section 2.1.4 highlights the challenges faced in the preparation of the core of the outlined target compounds. Following, section 2.1.5 outlines the successful generation of epi-(±)-tremulenolide A, epi-(±)-tremuelenediol A, and epi-(±)-ceriponol D.