I. Development of the asymmetric type 2 intramolecular acylnitroso Diels-Alder reaction. II. Studies toward the formal synthesis of bengamides

This dissertation focuses on the asymmetric type 2 intramolecular acylnitroso Diels-Alder reaction and its application in organic synthesis. Chapter 1 introduces the intermolecular Diels-Alder reaction and discusses the scope of the reaction. An overview of the type 1 and type 2 intramolecular Diels-Alder reactions follow. In Chapter 2, discussion will focus on the synthesis, reactivity, and applications of the nitroso dienophile. Specifically, the acylnitroso species will be reviewed in the context of nitroso ene reaction and acylnitroso Diels-Alder reaction.; Chapter 3 describes the stereoselective synthesis of bridged bicyclic oxazinolactams using the type 2 intramolecular acylnitroso Diels-Alder reaction. In these reactions, complete diastereoselectivity of the cycloaddition was observed when substituents were present in the tether of the hydroxamic acid Diels-Alder precursors. Elaboration of the cycloadducts liberated azepin-2-ones and azocin-2-ones.; Chapter 4 presents our development of asymmetric catalysis for the inter- and intramolecular acylnitroso Diels-Alder reactions. Chiral cyclohexyldiimine salen ligands were found to be effective for inducing enantiomer bias in the ruthenium catalyzed oxidation-cycloaddition of hydroxamic acids and N-hydroxycarbamates in high chemical yield and enantioselectivity up to 71%. Mechanistic insights of the transition metal catalyzed reaction based on reactivity results will be given.; The diversity and biological properties of bengamides are presented in Chapter 5. Survey of approaches to the successful syntheses of the bengamide alkaloids follows. Chapter 6 then describes our efforts in the synthesis of the caprolactam subunit in bengamide B using the type 2 intramolecular acylnitroso Diels-Alder reaction. A model study that led to the synthesis of a cis-2,6-disubstitued azepin-2-one in 91:09 diastereomeric ratio is presented.