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The Pennsylvania State University The Pennsylvania State University The Graduate School Department of Chemistry STUDIES TOWARD THE TOTAL SYNTHESIS OF STREPTORUBIN B A Dissertation in Chemistry by William Brent Clayton © 2008 William Brent Clayton Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy December 2008 ii The dissertation of William Brent Clayton was reviewed and approved* by the following: Ken S. Feldman Professor of Chemistry Dissertation Advisor Chair of Committee Gong Chen Assistant Professor of Chemistry Scott Phillips Assistant Professor of Chemistry Ronald Hedden Assistant Professor of Materials Science and Engineering Ayusman Sen Professor of Chemistry Head of the Department of Chemistry *Signatures are on file in the Graduate School iii ABSTRACT Streptorubin B is a member of the prodigiosin family of natural products which are receiving considerable attention from academia as well as the pharmaceutical industry for their novel immunosuppressive and cytotoxic properties. Despite this interest, little effort has been shown toward an asymmetric synthesis of streptorubin B or the relationship between its chirality and biological activity. Progress toward the asymmetric synthesis of streptorubin B and its stereoisomers is herein described. Alkynyliodonium salts are versatile substrates which have been used to form a variety of heterocycles and other ring systems. The alkylidenecarbenes generated from the addition of soft nucleophiles to alkynyliodonium salts can insert intramolecularly into carbon-hydrogen bonds and typically do so with a high degree of regio- and stereoselectivity. The C ring of streptorubin B was made using this branch of hypervalent iodine chemistry, but this route was later abandoned due to failure of subsequent steps and instability of the products formed. The challenges involved in forming medium sized rings with ring closing metathesis are beginning to be understood and in many cases have been overcome by conformation constraints. The possibility of using ring closing metathesis to close the bridging ten membered D ring of streptorubin B was explored. However, the enthalpy and entropy barriers for this conversion were determined to be too great to surmount. After other ring closing methods were investigated, a Nozaki-Hiyama-Kishi coupling was found to be successful. iv TABLE OF CONTENTS LIST OF FIGURES .....................................................................................................vi ACKNOWLEDGEMENTS.........................................................................................xii Chapter 1 Streptorubin B and Related Prodigiosins ...............................................1 1.1 Biological activity of prodigiosins..................................................................2 1.1.1 pH modulation. .......................................................................................3 1.1.2 Cell cycle inhibition................................................................................4 1.1.3 DNA cleavage.........................................................................................7 1.1.4 Other biological properties .....................................................................8 1.2 Biosynthesis....................................................................................................9 1.3 Structure: Confusion between streptorubin B and butylcycloheptylprodigiosin. ...........................................................................12 1.4 Published syntheses of prodigiosins. ..............................................................15 1.4.1 Rapoport’s synthesis of prodigiosin........................................................15 1.4.2 Boger’s sythesis of prodigiosin...............................................................18 1.4.3 Wasserman’s synthesis of the northern half of the prodigiosins. ...........20 1.4.4 Undecylprodigiosin.................................................................................21 1.4.5 Wasserman’s synthesis of metacycloprodigiosin. ..................................23 1.4.6 Fürstner’s synthesis of the core of metacycloprodigiosin.......................25 1.4.7 Fürstner synthesis of butylcycloheptylprodigiosin. ................................26 1.4.8 Reeves’ synthesis of butylcycloheptylprodigiosin..................................29 1.4.9 Nonylprodigiosin....................................................................................31 1.4.10 Lavallée’s synthesis of the northern half of the prodigiosins. ..............33 1.4.11 Fürstner’s synthesis of the core of streptorubin B. ...............................33 1.4.12 Murthy’s synthesis of streptorubin B....................................................35 1.4.13 Chang’s synthesis of the core of streptorubin B. ..................................37 1.5 Conclusions.....................................................................................................39 1.6 References.......................................................................................................40 Chapter 2 Project Plans and Goals..........................................................................46 2.1 Retrosynthesis.................................................................................................46 2.2 Backup plans...................................................................................................49 2.3 Biology and isolation ......................................................................................51 2.4 References.......................................................................................................52 Chapter 3 Alkylidenecarbenes ................................................................................54 3.1 Structure of alkylidenecarbenes......................................................................54 3.2 Formation of alkylidenecarbenes....................................................................55 3.3 Reactivity of alkylidenecarbenes....................................................................59 3.3.1 Additions to double bonds. .....................................................................60 3.3.2 1,2-Shifts.................................................................................................61 v 3.3.3 1,5-Insertions and additions....................................................................62 3.3.3.1 Carbon-hydrogen insertions............................................................62 3.3.3.2 Heteroatom-hydrogen insertions.....................................................69 3.3.3.3 Intermolecular heteroatom-lone pair additions...............................71 3.3.5.4 Intramolecular heteroatom-lone pair additions...............................73 3.4 Conclusions and application to streptorubin B...............................................77 3.5 References.......................................................................................................78 Chapter 4 Ring Closing Metathesis involving Medium Sized Rings .....................83 4.1 Difficulties in ring closing metathesis reactions involving medium sized rings. .......................................................................................................84 4.2 Conformation consequences in ring closing metathesis reactions. ................88 4.2.1 Substitutional Effects..............................................................................89 4.2.2 Fused polycycles.....................................................................................92 4.2.3 Bridged polycycles..................................................................................94 4.3 Examples of ring closing metathesis reactions forming medium sized rings..................................................................................................................99 4.3.1 Nine membered rings..............................................................................99 4.3.2 Ten membered rings. ..............................................................................102 4.3.3 Eleven membered rings...........................................................................107 4.4 Conclusions and application to streptorubin B...............................................111 4.5 References.......................................................................................................112 Chapter 5 Efforts toward a stereoselective synthesis of Streptorubin ....................118 5.1 Overview.........................................................................................................118 5.2 Synthetic methods...........................................................................................119 5.2.1 Attempts with alkynyliodonium salts ....................................................119 5.2.1.1 Intermolecular strategy..................................................................119 5.2.1.2 Intramolecular strategy..................................................................123 5.2.2 Attempts with Horner-Wadsorth-Emmons.............................................129 5.2.3 Attempts with ring closing metatheis. ....................................................131 5.2.4 Success with Nozaki-Hoyama-Kishi macrocyclization chemistry.........138 5.3 Conclusions and future work..........................................................................140 5.4 References.......................................................................................................142 Chapter 6 Experimentals.........................................................................................144
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