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Jones Isomers” BIOSYNTHETIC STUDIES OF OTTELIONE A AND THE STRUCTURAL RE-ANALYSIS OF THE “JONES ISOMERS” THE STRUCTURAL REASSIGNMENT OF PHOMOPSICHALASIN TO THAT OF DIAPORTHICHALASIN A DISSERTATION SUBMITTED TO THE FACULTY OF THE GRADUATE SCHOOL OF THE UNIVERSITY OF MINNESOTA By Susan G. Brown IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Thomas R. Hoye, Adviser February 2013 © Susan G. Brown 2013 Portions © J. Nat. Prod. 2012 and used with permission i ACKNOWLEDGEMENTS Firstly I would like to thank my adviser professor Thomas Hoye for his patience, guidance and mentorship throughout my time spent in his group. His keen ability to hone in on the details of the problem at hand has made me into the chemist that I am today. To professors Andrew Harned, Wayland Noland and Robert Fecik, thank you for serving as members on my committee as well as for the helpful conversations along the way. I would also like to thank my undergraduate adviser, professor Rebecca Hoye. Becky, your mentorship and willingness to always serve as a listening ear was truly indispensable both throughout my time at Macalester and the University of Minnesota. To my friends from the “consulate”, thank you for making Minnesota my home away from home for the past several years. Finally to my mother and father, Dothlyn and Albert, your unwavering love and support has enabled the completion of this thesis. Thank you for being devoted parents. ii DEDICATION To my mother and father, Dothlyn and Albert Brown. iii ABSTRACT Part I Ottelione A, isolated from the fresh water plant Ottelia alismoides, is a cytotoxic agent at nanomolar levels against 60 human cancer cell lines. Among other compounds isolated were a group of novel 1,7-diarylheptanoids. We propose that one of these diarylheptanoids shares a biogenetic linkage with ottelione A. Namely, we hypothesize that a spontaneous (i.e., non-enzyme catalyzed) Cope rearrangement, almost entirely unprecedented in nature, is central to the biosynthesis of ottelione A. The successful synthesis of the hypothesized biologically relevant diarylheptanoid has now enabled us to probe its possible biogenetic linkage to ottelione A. During the course of our studies we have also performed the structure reanalysis of two related hydrienone compounds that share the exact same core as ottelione A. Part II Phomopsichalasin, a cytochalasin-like secondary metabolite, was isolated from an endophytic fungus Phomopsis sp. in 1995. Diporthichalasin, from the endophytic fungus Diaporthe sp. Bkk3, was isolated several years later in 2007. Both were assigned different structures and their spectroscopic characterization reported in two different solvents. By way of detailed NMR analysis and pertinent computational models we have demonstrated that the structure originally proposed for Phomopsichalasin was incorrect and is in fact that of the more recently isolated compound Diaporthichalasin. TABLE OF CONTENTS Acknowledgements i Dedication ii Abstract iii Table of Contents iv-vi List of Tables vii-viii List of Figures ix-xii List of Abbreviations xiii-xv PART I : BIOSYNTHETIC STUDIES OF OTTELIONE A AND THE STRUCTURAL RE-ANALYSIS OF THE “JONES ISOMERS” Chapter I. A potential role for diarylheptanoids in the biosynthesis of ottelione A I-A. Introduction and Background I-A1. Isolation, structural characterization and biological activity of the otteliones 2-5 I-A-2. Biosynthetic hypothesis 5-9 I-A-3. Prior accounts of the Cope rearrangement in nature 9-13 I-A-4. Synthetic strategies toward otteliones A and B 14-15 I-B. Diarylheptanoids in nature I-B-1. Introduction 16-18 I-B-2. Synthesis of 177 and 178 19-24 I-C. Future Studies 25 I-D. Concluding remarks 26 Chapter II. The Cope rearrangement within the strained [m]-cyclophane 204-prox II-A. Background II-A-1. Introduction 27-29 II-A-2. First generation synthesis of 204-prox 29-32 II-B. Efforts toward the improved synthesis of 204-prox II-B-1. Synthesis of 209 – A chromatographic solution 33-34 II-B-2. A thiol-ene click strategy 35-39 II-B-3. Double β-alkyl Suzuki reaction 39-45 II-B-4. Intramolecular displacement of allyl halides 45-48 II-C. Progress toward the synthesis of [9]-paracyclophane 298 II-C-1. Synthesis of 2107 and attempted cyclization 49-50 II-D. Concluding Remarks 51 Chapter III. Flash vacuum pyrolysis experiments and the structural reassignment of the Jones Isomers III-A. Flash vacuum pyrolysis II-A-1. Introduction 52-54 II-A-2. Relevant FVP experiments 54-55 II-A-3. Synthesis and FVP of 321 55-71 III-B. Evidence in support of the structural reassignment of 322-endo to 323-endo and 323-endo to 323-exo. III-B-1. Computational support 72-73 III-B-2. Addressing the constitution of Isomer I: 322-endo vs. 323-endo 73-75 III-B-3. Relative configuration of Isomer II: 323-endo vs. 323-exo 76-79 III-B-4. Crucial NOE experiments 79-80 III-C. Concluding remarks 81 PART II : REASSIGNMENT OF THE RELATIVE CONFIGURATION OF PHOMOPSICHALASIN Chapter IV. The hexa-epimers phomopsichalasin and diaporthichalasin IV-A. Background IV-A-1. Introduction 83-85 IV-A-2. Biosynthetic hypothesis 85-87 IV-A-2. Spectroscopic ambiguity surrounding the structure assigned to phomopsichalasin 88-89 IV-B. Previous synthetic efforts IV-B-1. Progress towards the synthesis of ‘phomopsichalasin’ – Structure determination via synthesis 90-91 IV-C. A case for the structural reassignment of phomopsichalsin IV-C-1. Computational support 92 IV-C-2. Spectroscopic support 93-99 IV-C-3. Miscellaneous observations – dehydration and oxidative degradation of 402 100 IV-D. Concluding remarks 101 Experimental 102-183 Bibliography 184-191 vii LIST OF TABLES Table I-1. Half-life, temperature, and energy of activation (experimental and computational) of Cope rearrangement within 1,5-hexadiene (137), cis-divinylcyclopropane (130), and bullvalene (138); the known types of Cope rearrangement relevant to natural product biosynthesis [139 (pre-ectocarpene) to ectocarpene and 140 (vis-à-vis welwitindolinones and dragmacidin E)]. aDFT B3LYP/6-31G. bSCF-MO (MIND0/2). cOur estimate based on reported NMR data. dCalculated using this estimated t1/2 and the Arrhenius factor from the parent divinylcyclopropane 130…………………….…………..…………..11 Table I-2. NMR spectral data for 4-((1E,4E)-7-(4 hydroxyphenyl)hepta-1,4-dien-1-yl)-2-methoxyphenol (177) in CDCl3……………………………..…………………….….23 Table I-3. NMR spectral data for 4-((1E,4E)-7-(4 hydroxyphenyl)hepta-1,4-dien-1-yl)benzene-1,2-diol (178) in CDCl3……………………..………………………….....….23 Table II-1. Conditions screened in the quest of conducting the double β-alkyl Suzuki………………………….……….........….41 Table III-1. NMR spectral data for (1R,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-endo) in CDCl3......…………………………………..….……..63 Table III-2. NMR spectral data for (1R,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-endo) in methanol-d4……………………………...……….…..64 Table III-3. NMR spectral data for (1R,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-endo) in CDCl3, methanol-d4, and acetone-d6…...……….…....65 Table III-4. NMR spectral data for (1S,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-exo) in CDCl3......…………………………………..….…..…..66 viii Table III-5. NMR spectral data for (1S,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-exo) in methanol-d4.……………………………...…….….…..67 Table III-6. NMR spectral data for (1S,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-exo) in CDCl3, methanol-d4, and acetone-d6.…...……….….....68 Table III-7. NMR spectral data for (5aR,8aS)-1,2a1,4,5a,6,8a- hexahydroacenaphthylen-5(2H)-one in CDCl3.…...……….……......69 Table III-8. NMR spectral data for (5aR,8aS)-1,2a1,4,5a,6,8a- hexahydroacenaphthylen-5(2H)-one in methanol-d4.…...………......70 Table III-9. NMR spectral data for (5aR,8aS)-1,2a1,4,5a,6,8a- hexahydroacenaphthylen-5(2H)-one in CDCl3, methanol-d4, and acetone-d6.…........................................…….…......71 Table IV-1. NMR spectral data for diaporthichalasin (402) in d4-methanol (UMN)….…...………………………………....…....94 Table IV-2. NMR spectral data for diaporthichalasin (402) in d6-DMSO….…….…...…………………………………....….......95 Table IV-2. NMR spectral data for diaporthichalasin (402) in CDCl3….…….…...…………………………………....….............96 ix LIST OF FIGURES Figure I-1. Panel A. Structures of otteliones A and B; Panel B: p-cresol Tautomer RPR115781………………......…..……...………3 Figure I-2. Panel A. Hoye’s first proposal of the structure for ottelione A (101) Panel B. Hoye’s first proposal of the structure for ottelione B (102)……………….……………….....…...3 Figure I-3. Structure activity relationship of ottelione A…...…...………………4 Figure I-4. Collection of diarylheptanoids isolated by Hoye and coworkers…...……...………………………………………………..6 Figure I-5. Hoye and coworkers wonder if there was a biosynthetic linkage between compounds, 107 and 101…………………...……...6 Figure I-6. A small representative sample of natural products derived from the Diels-Alder cycloaddition………..………...……...9 Figure I-7. Conditions used for the epimerization of ottelione A (101) to ottelione B (102)…………..………………….…………..……...14 Figure I-8. The five types of 1,7-diarylheptanoids……...……..……..………...16 Figure I-9. Generic structures of families of diarylheptanoid (I), biarylheptanoid (II), anddiaryletherheptanoid (III) natural products………………..…………..…………..…………...18 Figure II-1. Panel A: Biosynthetic formation of ottelione A (101) from [m]-cyclophane 115. Panel B: Truncated analogous of 101 (202-exo) and 115 (201) lacking the benzyl substituent……………..…………..……..…..……...……...27 Figure II-2. Cope rearrangement with the strained compound 201 to 202-exo. 201 can be accessed from the K.E.T. from 203 that is made from the MOM-protected phenol 204-prox.……………..…………..……..…..……....……...28 Figure II-3.
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