Metathesis in Natural Product Synthesis

Preface SYNTHESIS OF NATURAL PRODUCTS CONTAINING MEDIUM-SIZE CARBOCYCLES BY RING-CLOSING ALKENE METATHESIS Introduction Formation of Five-Membered Carbocycles by RCM Formation of Six-Membered Carbocycles by RCM Formation of Seven-Membered Carbocycles by RCM Formation of Eight-Membered Carbocycles by RCM Formation of Nine-Membered Carbocycles by RCM Formation of 10-Membered Carbocycles by RCM Conclusion NATURAL PRODUCTS CONTAINING MEDIUM-SIZED NITROGEN HETEROCYCLES SYNTHESIZED BY RING-CLOSING ALKENE METATHESIS Introduction Five-Membered Nitrogen Heterocycles Six-Membered Nitrogen Heterocycles Seven-Membered Nitrogen Heterocycles Eight-Membered Nitrogen Heterocycles Conclusion SYNTHESIS OF NATURAL PRODUCTS CONTAINING MEDIUM-SIZE OXYGEN HETEROCYCLES BY RING-CLOSING ALKENE METATHESIS Introduction General RCM Approaches to Medium Rings Laurencin Eunicellins/Eleutherobin Helianane Octalactin A Microcarpalide and the Herbarums Marine Ladder Toxins Conclusion PHOSPHOROUS AND SULFUR HETEROCYCLES VIA RING-CLOSING METATHESIS: APPLICATION IN NATURAL PRODUCT SYNTHESIS Introduction Synthesis and Reactivity of Sulfones Derived from RCM Total Synthesis of the Originally Proposed Structure of (±)-Mycothiazole Synthesis and Reactivity of Phosphates from RCM Applications of Phosphate Tethers in the Synthesis of Dolabelide C Conclusion SYNTHESIS OF NATURAL PRODUCTS CONTAINING MACROCYCLES BY ALKENE RING-CLOSING METATHESIS Introduction Organization of the Chapter Macrocyclic Polyketides Terpenoids Macrocyclic Lipids Macrocyclic Glycolipids Conclusions and Outlook SYNTHESIS OF NATURAL PRODUCTS AND RELATED COMPOUNDS USING ENE-YNE METATHESIS Introduction Synthesis of Natural Products and Related Compounds Using Ene-Yne Metathesis Synthesis of Natural Products and Related Compounds Using Ene-Yne Cross-Metathesis (CM) Synthesis of Natural Products Using Skeletal Reorganization RING-CLOSING ALKYNE METATHESIS IN NATURAL PRODUCT SYNTHESIS Introduction Alkyne Metathesis Ring-Closing Alkyne Metathesis Applications of RCAM in Natural Product Synthesis Conclusions TEMPORARY SILICON-TETHERED RING-CLOSING METATHESIS REACTIONS IN NATURAL PRODUCT SYNTHESIS Introduction Temporary Silicon-Tethered Ring-Closing Metathesis Reactions Conclusions and Outlook METATHESIS INVOLVING A RELAY AND APPLICATIONS IN NATURAL PRODUCT SYNTHESIS Introduction Early Relay Metathesis Discoveries Examples of Relay Metathesis Directed at Targets Other tan Natural Products Examples of Relay Metathesis Motivated by Natural Product Synthesis Examples of Relay Metatheses Thwarted in Achieving the Desired Outcome Conclusion CROSS-METATHESIS IN NATURAL PRODUCT SYNTHESIS Introduction Functionalization of Olefins Appending a Side Chain Couplings Cascade Processes Involving CM Ene-Yne CM Alkyne CM Conclusion and Perspectives CASCADE METATHESIS IN NATURAL PRODUCT SYNTHESIS Introduction RCM-CM Sequences Ene-Yne-Ene RCM-RCM ROM-CM Sequences RCM-ROM Sequences - Ring-Rearrangement Metathesis (RRM) RCM-ROM Sequences Combined with Other Metathesis Reactions Conclusions and Outlook CATALYTIC ENANTIOSELECTIVE OLEFIN METATHESIS AND NATURAL PRODUCT SYNTHESIS Introduction Total Synthesis of Natural Products with Enantiomerically Pure Chiral Olefin Metathesis Catalysts Bearing a C2-Symmetric Diolate Ligand Enantioselective Synthesis of Quebrachamine through an Exceptionally Challenging RCM Reaction Synthesis of Baconipyrone C by Ru-Catalyzed Enantioselective ROCM Conclusions and Future Outlook METATHESIS REACTIONS IN SOLID-PHASE ORGANIC SYNTHESIS Introduction Metathesis-Based Cyclorelease Reaction Ring-Closing Metathesis (RCM) Intraresin Dimerization Restricting Peptide Conformation through Cyclization Cross-Metathesis on Solid Phase Ene-Yne Metathesis on Solid Phase Conclusion