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Furanosesquiterpenes from Eremophila Rotundifolia : A

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Furanosesquiterpenes from Eremophila Rotundifolia : A FURANOSESQUTTERPENES FROM EREMOPHTLA ROTUNDTFOLTA A STRUCTURAL, STEREOCHEMICAL AND SYNTHETTC INVESTIGATTON A Thesis pnesented fon the degnee of Docton of Philosophv l_n The University of Adelaide by Eugene Dimitriadis, B.Se. (Hons. ) Department of Organic Chemistry August, 1980 rl"t¡*J)t'î\8f *uNJ"( Tabl-e of Contents Page SUMMARY i STATEMENT ii ACKNOIÀTLEDGEMENTS iii INTRODUCTÏON 0.1 Genenal- 1 0.2 Furanosesquitenpenes 3 0.3 Tenp enes in Eremophila s pecies 10 CHAPTER 1 THE STRUCTURE OF EREMOACETAL 1.0 Spectral Data Leading to the Gross Stnucture 19 1.1 The Steneochemistry of Eremoacetal 2L CHAPTER 2 . RING OPENING REACTIONS OF EREMOACETAL AND ITS DERIVATIVES 2.0 Genenal- 29 2.1 Acid Catalysed Hydnolysis 30 2.2 SoJ-volysis Under Basic Conditions 50 2.3 Binch Reductions 52 2.4 Diborane Reductions 64 2.5 Hydnide Reductions 69 CHAPTER 3 - THE SYNTHETIC UTILITY OF EREMOACETAL 3 0 Genenal 77 3 1 0smium Tetnoxide Reaction 7,8 3 2 m-Chl-oropenbenzoic Acid Reaction 80 3 3 Oxidation of 1 r 2-diols 82 3 4 Diborane Reaction 83 3 5 Oxymencunation Reaction 84 3 6 Sulphun Y1ide Reaction 85 3 7 Gnignard Reactions 88 I CFIAPT ER 4 - THE SYNTHESIS OF SOME NATURAL PRODUCTS USING EREMOACETAL 4.0 Genenal B9c 4.1 ( - ) -oefrydnongaione 89e 4.2 ( + ) -rpingaione 90 4.3 ( R, E-) - 4-Flydroxymyoporone (Athanograndione ) and 9t_ Ipomeanine 4.4 Othen Oxidation Products of Alcohol-s 94 CHAPTER 5 - THE STRUCTURE AND SYNTHESIS OF (S)-4-HYDROXY- DENDROLASIN FROM EREMOACETAL 5.0 Spectnal Data Leading to the Gross Structune 97 5.1- Reduction to Dendnolasin 99 5.2 Oxidation to Dihydrophymaspermone 99 5. 3 Oxmer:cunation and Epoxidatíon Reactions r02 5.4 Synthesis fnom Er:emoacetal 103 5.5 Steneochemistny 105 CHAPTER 6 -THE STRUCTURE AND SYNTHESIS OF (E)-7-METHYL-7- ( 4I -METI]YLPENTA_f 3 ' -DTENYL) -4 ,5 ,6 ,7- TETRAÌ{Y DRO BEN Z O FU RAN" 6.0 Spectna and Stnuctune of the Diene 106 6.1 Synthesis fr.om Eremoacetal 108 6.2 Hydrogenat-ion of Diene using P2-Ni 110 CHAPTER 7 SYNTHES]S OF FUROSPONGTN-f 7 0 General II2 7 I Synthetic Pl-an 116 118 7 2 Synthesis of the Cg and Cg Halides 12B 7 3 Reactic¡n of Aldehyde with various Nucleophiles 7 4 \^littig Reaction 128 7 5 Hydrogenation and Ring Opening 130 7 6 Dehydration and Sepanation of Isomens l-32 7 7 Some Further Investigations t_36 l- l_ CHAPTER B - STERIC EFFECTS IN TIOREAUIS METHOD OF DETERMINING ABSOLUTE CONFIGURATION 8.0 Genenal 141 B;1 Aim of the Study 142 8.2 Principles Behind Horeauts Pnocedune and the 143 Bnooks and Gilbent lvlodification. 8.3 Applieation of the G.C. Method to the Al-cohols 144 8.4 Tabl-es of Results and þiscussion 148 8.5 Concl-usion 164 EXPERTMENTAL 1-67 Appendix (A) r 3c n.m.r, data 286 Appendix (B) Spectnal D.ata for Tenpènes fnom Heantwood 300 of E. rotundifol-ia REFERENCES 301 SUMT4ARY The l-eaves and twigs of E. notundifolia provided a numbe:r of 3-funano-sesquitenpenes. Among the known compounds isol-ated were dendnolasin, (E) and ( z ) -aifrydnophymaspelrmones , dehydro- ngaione and dehydnoepingaione. Some of the sesquiterpenes isol-ated which had not been previously descnibed included (S rø)-4-hydnoxydendrolasin (B) and an unstable tetrahydnobenzo- fur-an diene (46) with a novel- skefeton. A majon plant constituent r^ras a stabl-e and crystalline bicyclic acetal- which contained three centnes of chirality. The greater part of the thesis descnibes the stnuctune, stereochemi-stry, reactions and utility of enemoacetal- (47) as a useful chiral- pnecurson to a numben of other funanoterpenes. 'lelrahgdro A synthesis of the benzofunan diene (46) uia a cationi c A intenmediate denived from the dihydnophymaspelrmones, confirmed the stnucture of this sesquitenpene. (S rn)-4-Hydnoxydendrolasin (B) was synthesised fnom elremo- acetaf confirming the stnuctune and steneochemistny of (B). Most inportantty the synthesis confirmed the nesults obtained fnom the appJ-ication of Horeaurs technique to this a.l.coho.l . lrlhile exploring the ring opening of the acetal function, some interesting neactions were obse::ved and investigated. In a,.d. panticufar, the acidic and basic hydrolysis, the Binch reduction A h/er?e examined with elîemoacetal and cer.tain derivatives. The nesul-ts fnom these investigations all-owed the conversion of eremoacetal- into a vaniety of highly functionalised compounds of pnedictable stereochemistry. These pnoducts ü/ere utilised in the pr.eparation of a numben of furano-sesquiterpenes. rn this waYr in addition to 4-hydnoxydendnolasin, (-)-dehydnongaione, (+)-epingaione, ipomeanine and (-)-athanagnandione welre synthe- sized. The pnepanation of (-)-(S)-athanagrandione allowed the previousry unknown steneochemistny to be detenmined. Util-ising the p::eviously exploned neactions of eremoacetal and its derivatives a synthesis of (-)-furospongin-l, a czr difunanoterpene, was completed fon the finst time. A number of useful fuçospongin-I doubte bond isome:rs and epimens r^ras concur?r?ently synthesised. These isomers proved useful in a study of Hor.eaur s method panticuranly with nespect to stenic effects in the determination of absolute configunation. The epimens of each double bond ísomen hreue obtainecl in an enantio- menically pure fonm. Iloweven, the synthetic (-)-furospongin-ì_ hras contaminated with its inseparable epimen. This synthesis hlas valuable in that it demonstrated the utility of enemoacetal denivatives as useful chinal templates. Finally r el?emoacetal was used to synthesise a wide vaniety of enantiomerically pur.e secondary alcohols of known steneo- chemistny. These alcohol-s Ì,vene then usecl in a study of effec- tive stenic size of substituents about the chiral- centr:e beaning the secondary hydnoxyl group by the application of Iloneaurs method. The study was cannied out using the g.c. modification of Honeauts method allowing some conclusions to be made as to the effective sizes of va:rious substituents. Some of the limitations of the B. c. modified technique wel?e ovel?come and h. p. I . c . \^ras shown to be a good altennative procedune. The appendix incl-udes a list of 13C r,.m.r. spectnal data of vanious nelated bicyclic, monocyclic and acyclic com- pounds presented in a systematic, tabul-ar? mannen to show the infl-uence of substituents, stnucture and steneochemistry upon chemical shift. (ii) STATEMENT This thesis presents the wonk of the authon duning the peniod 1977 to 1979 in the Depantment of Onganic Chemistny at the Univensity of: Adelaide. This thesis contains no matenial previously submitted fon a degree on diploma in any univensity, and to the best of my knowledge and belief, contains no material pneviously published on wnitten by anothen person, except whene due refenence is ,made in the text, (Eugene Dimitniadis) ACKNOWLEDGEMENTS To Dr. R.A. Massy-ldestnopp I wish to expness my sincene gratitude fon his intenest, encourragement, and guidance extended to me duning his supenvision of this wonk. He has extended my appreciation of new fields of chemistry fon which I am veny thankful. I am al-so gnatefuJ- to Dn. D. P. G. Hamon f or his supen- vision and intenest during pant of this wonk and to the other membens of the Organic Chemistny Depantment with whom I had helpfuJ- discussions. In panticular, I am sincenely appneciative of the tolerant and loving suppont of my wife Many. I am al-so grateful to my typist fon her diligence and effor.t. This r"eseanch was cannied out during the tenur:e of a Commonwealth Post-Graduate Research Awand, which I gnatefully acknowledge. 2 fH H OPP OPP b (2) ( 3) H H f OPP b (4) AJ-though the biosynthetic pathway has been extensively studiedt 2 necent work has given funthen infonmation about the condensation of the two pynophosphates (2) and (3).rG The presently accepted view j.s that (2) and (3) condense in a highly stereospecific mannen, pnobabÌy in a canbonium ion like pnocess, to fonm geranyl pynophosphate (4). It has been shown that the furthen condensation of Q) with (4) then occurs with inversion at Cf, and the pro-E hydrogen (Ha) of (2) becomes 'Elne pro-^9 hydnogen of farnesyl pyrophosphate. (Crs) (5). Monotenpenes (Clo), the volatile and odoniferous con- stituents of rûany fnuits, flowers and other parts of many plants, al?e derived fnom genanyl pyrophosphate (4). Fannesyl pynophosphate (5) is the preculîson to sesquiterpenes (C15) Sinifan such condensations lead to genanylgeranyl p.ynophos- phate (C20) which l-eadsto ditenpenes. The intermediate pynophosphates can undengo a senies of enzyme mediated solvol-y- ses (sce Fig. 1) which gives nise to cyclisedrdimerisedl nearranged and further functionalised tenpenes. Such a poly- merisation scheme invoÌving the panent acylic C5 compounds nesulting in the familan rhead to tailr pattenn of unrealrllanged Fie. I (2) OPP C5 hemitenpenes P (3) + (3) PP Clo monoterpenes (+) ----+ +(3) C r s sesc¡uitenpenes dimerisation Cg o tritenpenes OPP { steroids (s) Czo ditenpenes PP (3) Czs sestenpenes --.-.--È dimerisation OPP =pyrophosphat e Carotenoi-ds J tenpenes, has been cal-led the Biogenetic Isoprene Rul-e. Tenpene skel-etons anising fnom llearnangement and/or degnadation alîe of particulan interest, such as the stenoids, the enemophir"n"å6and recently the Czt funospongin gnoup53's6 0.2 Furanosesquiterpenes A lange gnoup of furanoterpenes has been found which contain 3-substituted funan nings and some are of interest because of their toxicity.TT-2 0 Such furanoterpenes occun in animal-s (ants,"u tenmites"), manine onganismsr" tnopical treesr2q and infected tuberstez2Q)25 as wel-l- as in some Austral-ian plants .r7 )rs )26 A common feature of these sesquitellpenes is thejn speciJ f ic sites of oxygenation. This is il-lustnated by an exami-n- ation of dendrol-asin (6) a simple monoxygenated nemben of this series.
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