Palladium-Catalyzed Oligocyclizations of Some 2-Bromotetradec-1-ene-7,13-diynes Under Heck Reaction Conditions

Abstract

Ich möchte an dieser Stelle meinem Lehrer, Herrn Prof. Dr. Armin de Meijere, danken für die interessante Themenstellung, die Unterstützung und die vielen Anregungen und Diskussionen während der Promotionszeit. To my parents ContentsA. Introduction 1. Cross-coupling reactions 2. Cycloisomerizations 3. Heck reactions 4. Cascade reactions B. Main Part 1. Palladium-catalyzed oligocyclization of 2-bromo-14-phenyltetradec-1-ene-7,13-diyne 1.1. Prologue 1.2. Synthesis of phenyl-substituted precursors 1.3. Palladium-catalyzed oligocyclizations of phenyl substituted precursors 2. Palladium-catalyzed oligocyclization of 2-bromo-14tert-butyldimethylsilyltetradec-1-ene-7,13-diyne 2.1. Prologue 2.2. Synthesis of tert-butyldimethylsilyl-substituted precursors 2.3. Palladium-catalyzed oligocyclizations of tert-butyldimethylsilyl-substituted precursors 3. Palladium-catalyzed oligocyclization of terminally alkoxycarbonyl-substituted of 2-bromotetradec-1-ene-7,13-diynes 3.1. Prologue 3.2. Synthesis of the alkoxycarbonyl-substituted precursors 3.3. Palladium-catalyzed oligocyclizations of alkoxycarbonyl-substituted precursors 3.4. The mechanism of the palladium-catalyzed oligocyclization of the alkoxycarbonyl-substituted precursors 4. Palladium-catalyzed oligocyclization of terminally alkoxycarbonyl-10-(2-bromoallyloxy)-1,7-decadiyne 4.1. Prologue 4.2. Synthesis and oligocyclization of the alkoxycarbonyl-substituted heteroatom-tethered precursor 4.3. The mechanism of the palladium-catalyzed oligocyclization of the heteroatom-tethered precursor 5. Palladium-catalyzed oligocyclization of terminally acetyl-substituted 2-bromotetradeca-1-ene-7,13-diynes 5.1. Synthesis of acetyl-substituted precursors 5.2. Palladium-catalyzed oligocyclizations of the acetyl-substituted precursors and their mechanism 6. Palladium-catalyzed oligocyclization of 2-bromotetradec-1-ene-7,13-diyne