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Table of Contents
1.0 Introduction.................................................................................................................... 1
1.1 The Role of Diversity-Oriented Synthesis in Modern Biomedical Research... 1
1.1.1 Transition Metal-Catalyzed Reactions in Diversity-Oriented Synthesis.9
2.0 Design and Synthesis of the Pivotal Intermediates ................................................... 15
2.1 Design of the Pivotal Intermediates................................................................... 15
2.2 Synthesis of the Pivotal Intermediates .............................................................. 17
2.2.1 Synthesis of Allenic Amino Esters............................................................. 17
2.2.1.1 Claisen Rearrangement via an Oxazole............................................ 17
2.2.1.2 Ester-enolate Claisen Rearrangement .............................................. 20
2.2.2 N-Alkylation of Allenic Amino Esters....................................................... 26
3.0 Synthesis and Use of Cross-Conjugated Trienes....................................................... 30
3.1 Transition Metal-Catalyzed Ene-type Cycloisomerization Reactions ........... 30
3.1.1 Allenic Cycloisomerization Reaction......................................................... 33
3.2 Rhodium(I)-Catalyzed Allenic Cycloisomerization Reaction of Amino-Ester
Tethered Allenynes ............................................................................................. 37
3.2.1 Preparation of Enol-ether Trienes via an Allenic Cycloisomerization
Reaction ...................................................................................................... 41
3.3 Diversification of Cross-Conjugated Trienes via Diels-Alder Reaction ........ 46
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