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Similas05031.Pdf Copyright by Suvi Tuula Simila 2008 The Dissertation Committee for Suvi Tuula Simila Certifies that this is the approved version of the following dissertation: Applications of Ring-closing Metathesis in Construction of Alkaloid Natural Products: Synthetic Studies on the Immunosuppressant FR901483 and Lundurines A-C Committee: Stephen F. Martin, Supervisor Philip D. Magnus Michael J. Krische Sean M. Kerwin Jennifer S. Brodbelt Applications of Ring-closing Metathesis in Construction of Alkaloid Natural Products: Synthetic Studies on the Immunosuppressant FR901483 and Lundurines A-C by Suvi Tuula Simila, M. S. Dissertation Presented to the Faculty of the Graduate School of The University of Texas at Austin in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy The University of Texas at Austin May 2008 Dedication Omistan väitoskirjani rakkaille vanhemmileni Sirkka Liisa ja Jukka Antero Similälle Acknowledgements I am sincerely grateful to my supervisor Prof. Stephen F. Martin for his continuous support, guidance and encouragement during my challenges in graduate school. He has taught me the most valuable skills, and the concept of critical thinking needed for becoming a successful synthetic chemist. The content of my dissertation would not exist without his guidance. I am indebted to Dr. Robert C. Andrews, my supervisor at Transtech Pharma, Inc., for guiding me to the best possible direction to obtain my graduate degree. I have had the pleasure to work with the most talented colleagues over the years in the Martin group, especially with Dr. Chi-Li Chen, Dr. Christopher Dockendorff, Ms. Anna Smith, and Mr. Michael O‟Keefe, who have not only been there for me during my professional challenges but who would also go above and beyond as my dear friends. I want to thank John DeLorbe, Mike O‟Keefe, Charlie Shanahan, and Daniel Knueppel for proofreading my dissertation. I thank my entire family, my parents Sirkka and Jukka, and my brothers Antti and Jarkko for all of their support, encouragement and for their faith in me as becoming the first doctor in the family. Especially, I‟m indebted to my grandparents, Liisa and Reino Oinas, who have made it possible for me to visit my family in Finland over the years by supporting me financially. I want to thank all my friends, and especially express my sincere gratitude to Victor Dixon and Christopher Friske for opening doors to their beautiful home for me and my family. Lastly, but most importantly, I am forever thankful to Trevor Orr for being by my side through this journey in graduate school. He has made me laugh every single day, through shine and rain. He has brought joy and happiness to my life. Forever grateful. v Applications of Ring-closing Metathesis in Construction of Alkaloid Natural Products: Synthetic Studies on the Immunosuppressant FR901483 and Lundurines A-C Publication No._____________ Suvi Tuula Simila, Ph. D. The University of Texas at Austin, 2008 Supervisor: Stephen F. Martin Ring-closing metathesis (RCM) has proven to be a valuable tool for constructing alkaloid-like, poly-cyclic compounds. The syntheses of alkaloid structures we were interested in developing, could utilize RCM to construct a spirocyclic structure for the immunosuppressant FR901483 and the tetracyclic framework of lundurines A-C asymmetrically. The azaspirane core of FR901483 was obtained via an addition of an allylsilane to an N-acyl iminium ion, and a RCM. Other key functional group manipulations were a stereoselective hydroboration and a subsequent lactonization that provided a precursor for a lactone-lactam rearrangement. This rearrangement provided the azatricyclic core of FR901483. In the enantioselective approach to FR901483 a new mildly cleavable protecting group was developed. Addition of a zinc nucleophile to a chiral N-acyl iminium ion, and a RCM provided the desired precursor for the hydroboration/lactone- lactam rearrangement sequence but without a sufficient stereoselection. vi A novel approach toward the total synthesis of lundurines A-C has been developed. The key features of the approach involve an intramolecular cyclopropanation of the indole C(2)-C(3) double bond, an enantioselective tandem RCM to construct the tetracyclic core and a concise synthesis to access the RCM precursor. An Ugi reaction was utilized with both cyclic and acyclic ketones, 2-vinyltryptamine derivative, a carboxylic acid and an isocyanide to access diverse compounds, including RCM precursors. An alternative reductive amination route to construct the RCM precursor for the lundurines was found to be more efficient and high yielding than the Ugi approach. An RCM was utilized to affect the closure of the five-and eight-membered rings of the tetracyclic core. This constitutes as the first example of RCM of a 2-vinylindole derivative to give an indole-fused eight-membered ring. vii Table of Contents Chapter 1: Ring-closing Metathesis in Alkaloid Synthesis ................................1 1.1. Introduction ............................................................................................1 1.2. Ring-closing Metathesis (RCM) ............................................................2 1.2.1. Ruthenium and Molybdenum RCM Catalysts .....................2 1.2.2. Mechanism of RCM .............................................................4 1.2.3. Heterocyclic Medium Size Rings by RCM .........................6 1.3. RCM Leading to Spirocyclic Structures ..............................................10 1.3.1. Spirocyclic Carbocycles via RCM .....................................10 1.3.2. Oxospirocyclic Structures via RCM ..................................13 1.3.3. Azaspirocyclic Structures via RCM ...................................14 1.4. Asymmetric Ring-closing Metathesis (ARCM) ..................................21 1.4.1. Chiral RCM Catalysts ........................................................21 1.4.2. ARCM Leading to Heterocyclic Structures .......................24 1.5. Applications of RCM to Alkaloids ......................................................32 1.5.1. Ircinal A and Manzamine A ...............................................32 1.5.2. Apogeissoschizine..............................................................34 1.5.3. Ergoline ..............................................................................35 1.5.4. (+)-FR900482 ....................................................................38 1.5.5. Tabersonine ........................................................................39 1.5.6. Oxindole Alkaloids ............................................................41 1.5.7. Mitralactonine ....................................................................43 1.5.8. Methyllycaconitine Analogues ..........................................44 Chapter 2: Synthetic Studies toward the Immunosuppressant FR901483.....46 2.1. Introduction ............................................................................................46 2.1.1. Isolation and Biological Activity .......................................46 2.1.2. Previous Syntheses and Approaches to FR901483 ............49 2.1.3. Previous Work in the Martin Group ..................................72 2.1.4. Retrosynthesis of FR901483 ..............................................79 viii 2.2. Results and Discussion ..........................................................................81 2.2.1. Model Studies ....................................................................81 2.2.1.1. Additions to N-Acyl Iminium Ions ................................81 2.2.1.2. Preformation of the Imine ..............................................85 2.2.1.3. RCM to Access the Azaspirane .....................................91 2.2.1.4. Hydroboration ................................................................93 2.2.1.5. Lactone-lactam Rearrangement ...................................101 2.2.2. Enantioselective Studies ..................................................103 2.2.2.1. Attempts to Form the Chiral Imine ..............................103 2.2.2.2. Development of a new protecting group ......................108 2.2.2.3. Development of a Zinc Nucleophile ............................115 2.2.2.4. Addition of the Zinc Reagent to the Chiral Imine .......119 2.3. Conclusions ..........................................................................................122 Chapter 3: Synthetic Studies toward Lundurines A-C ..................................128 3.1. Introduction ........................................................................................128 3.1.1. Isolation and Biological Activity .....................................128 3.1.2. Studies on the Framework of Lundurines ........................129 3.1.3. Retrosynthesis of Lundurines A-C...................................130 3.2. Results and Discussion ........................................................................133 3.2.1. Ugi Route to the Ring-closing Metathesis Precursor .......133 3.2.1.1. Ugi Reaction ................................................................133 3.2.1.2. Synthesis of the Amine Component ............................136 3.2.1.3. Syntheses of the Masked Divinyl Ketones ..................140 3.2.1.4. The Ugi Reaction with Ketones ...................................143 3.2.1.5. Synthesis of the RCM Precursor via Ugi Reaction ......163 3.2.1.6. Staudinger Reactions to Access the Ketimine .............169 3.2.2. Reductive Amination Route to the RCM Precursor ........172 3.2.2.1. Synthesis of the Divinyl Glycine Coupling
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