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Derivatives of Iceane : a Study in Molecular Architecture

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Derivatives of Iceane : a Study in Molecular Architecture 23.t\'87 DERIVATIVES OF ICEAIIE: A STUDY IN MOLECULAR ARCHITECTURE A Thesis Presented for the Degree of Doctor of Philosophy in TTIE T'NIVERSITY OF ADELAIDE by PauL Raynond Spunr, B.Se.(Hons.) Department of Organic Chenistry L982 (ii¡ OONTENTS SUMMARY (iv) STATE MENT (vi) ACKNOI^ILEDGEMENTS (vii) P RE FACE (vr-r-r-) CHAPTER ONE Studfes directed towards a flnal constructlon of the Lceane skelet,on by a sequentlal bond forning process. 1.1 Procedures Lnvolving Diels-Alder reactLons 2 between dienes and benzoqufnones. L.2 A procedure lnvolvfng a Dlels-Alder reactfon 30 between an o-xylylene and ¡ualeic anhydride. CHAPTER TIitO Studies concernfng a final construction of the iceane skeleÈon by a simulCaneous bond formfng process. 2.L Procedures Lnvolving Diels-Alder reactions 37 of tetrachlorothlophene dloxide with lsotetralln and propellanes. 2.2 The synÈhesls of reagents 1n Sectlon 2.I 63 (iii) CHAPTER THREE A rnf scellany of approaches. 3.1 Some heterocycllc examples. 72 3.2 Procedures based on an Aldol-type reacËion. 81 3 .3 Procedures based on a pfnacol-type reacÈfon. 9L CITAPlER FOUR Experl.¡nental. 4 .1 General. 97 4.2 [{ork descrf bed Ln Chapter One. 101 4.3 I{ork descrf bed in Chapter Two. r24 4.4 I{ork descrlbed Ín Chapter Three. 159 REFERENCF,..q L64 PI]BLTCATIONS L82 FRß.ÂT t83 (Ív) SUMMARY The construction of the tetracyclo[5.3 .L.L2'6.04' 9ldodecane (iceane) system (I) was approached according to the straÈegies outlined in the scheme below. II I H III H- H Scheme In chapter one' a rnet,hod is discussed for converting substructure (III) to (r) by a sequent,ial bond forming process whích involves a double intra- molecular alkylation reactÍon. Two precursors to a key interrnediate based on substructure III were prepared by two types of intermolecular Diels-Alder reactíons. The cis stereochemistry at the ríng junct,ion was generated by a cycloaddition reaction becween benzoquinone and a suitable diene. It was hoped that this st.ereochemistry would conÈrol the introduction of the remaining stereochemical requirements. rn an alternative approach, the cis orÍentaEion of the side groups r"las achieved by a cycloaddítion reaction between an o-xylylene and maleic anhydride. However, both of these reactions involved the formation of a teErasubstituted double bond which could not, be removed satisfactorily Ëo give the stereochemistry necessary for the trans- formati.on of substruccure (III) to (I). In chapter two, a method is discussed for converEing substructure (tlt) to (I) by a símultaneous bond forming process r¡hich involves an intramole- (v) cular Diels-Alder reactÍon. This required the Íncorporation of an exÈra ring system i-nto subsËructure III. The stereochemÍstry of one of the rÍng junctions ín this new subsÈrucÈure hras controlled by an inÈermolecular Dlels-Alder reacËion between a regenerabl-e diene and an approprÍate bis- dienophile. The correct sÈereochemistry at the other ring junction r¿as obtained only after a series of ínvestigatÍons in which lt was íntroduced either into Ëhe bÍsdienophlle before, or into the product obtained afËer, the inÈermolecular Diels-Alder reacÈion. The former procedure has allowed the preparation of a number of molecules Èhat contain the iceane skeleton. Some novel chenistry rüas encountered in the converslon of these compounds to derivatÍves of Íceane. In chapter three, a míscellany of related rouËes was investigaËed that was hoped would lead to a variety of iceane derívatfves including some dÍazaiceane compounds. Although interesËfng chemíst.ry has been revealed by these studies, none of the procedures r^ras successful in pro- viding the target compounds. (vi) STATBMENT Thts thesfs contalns no nateriar prevfously subml-tted for a degree Ln any Unl.versLty, and to the best, of ny knowredge and berfef, contaf.ns no material prevLousry published or wrftten by another person except ¡¡here due reference ls made ln the text. XT.t¿.re Paul Spurr. (vi1) ACKNOWLEDGE }IENTS I wish to express ny sfncere thanks Ëo Dr D.p .G. Hamon for hfs advlce and encouragement durfng the supervl.sÍon of this work. The helpful asslstance and suggestions from other members of the Depar t,ment are also acknow.Iedged . i Thts research rpas conducted durlng the tenure of a I Common¡¡ealth Postgraduate Award, for whfch I an grateful. I I I r an indebted to my typfsts, Mrs pat coe and Miss Julie Taylor, and to ny family for thelr patfence, tolerance and care duríng the course of my studies. l (vili) I l I i PREFACE The work presented ln thls thesfs does not repiesent a chronologlcar accounÈ of the chenistry developed in the course of thfs research. Rather, the format is constructed to best suit the discusslon of ideas report,ed hereln. consequentry, some sections, êspegrarry Èhose begun towards the end of this proJect, are incomplete. The actual order 1n whfch the research has been carrLed out was parts 1.1, 3.2, 2.I12.2, L.2, 3.3 and 3.1. There was, of course, aome overlap between sectlons. 1 CHAPTER ONE 2 1. I The highly symmeÈric (pofnr group D3t ) cage strucÈure, têÈracyclo t5.3.I.12,u .ou,t l dodecane (1) was I origfnally conceLved l_n I940 by MuIler . In 1965, 2 FLeser , upon examlnlng a nodel of a sectl.on of an fce crys Èal conEaining Èwelve water molecules (2) , fndependently pos tulated the existence of the hydrocarbon (I) with an analogous conflguratf.on havfng Èhe formula 3 CfZHte . The compound was approprLately named lceane 3 6 o'Å 9 t 7 H I I , '-o/'I I l0 TI I I (t) 2 lt SLnce Èhen, three separat,e synÈheses of fceane have appeared and slx other subs tances thaE lncorporate Èhe lceane framervork have also been reported: hexagonal 5 dlaroond f ound 1n some met,eorlÈes, the heptacycllc 67 compound (3) , the fused adamantane-l-ceane sys tem (4) , I a pyrolysls product of teÈrauerhyls llane (5) and the )t"-" and (ro)tu A molecular model of lceane appears to have a stable sCraln-free sÈructure slmllar Eo thaÈ of adamanÈane and tr¿lsÈane. 3 (3) (4) c H3 I (a) H3 X o (b) NH cHg H3 CH¡ \.r, H3 (6) (s) Ilowever, of the fLve slx-membered rlngs Ln the Lceane skeIeEon, tvo are ln Ëhe chair and three are ln the non- twfst boaE conflguratlon. This makes Èhe structure of lceane partlcularly LnÈeresting frorn an archfË.ecturaI point of view because, on account of thls unusual arrangement of atoEs, the molecule contains corisiderable non-bonded' interactions which have to be taken into account when deslgning a synthesis. 4 I n each of the prevlous syntheses of derivatlves of lceane, only one functlonal group has been l-ncorporate d lnto fhe nolecule. It was expected EhaÈ the preparaÈion of fceane derivatlves Èhat were dlfunctlonallzed at t.he ts¡o flagpole positfons of one of Ehe rlngs whlch 1s ln Èhe lnflexlble boat conflguraÈ1on would lnÈroduce non-bonded lnteracEfons more severe Ehan were already presenÈ. These compounds would have unusual physlcal and chemi ca I 4 propertles as Lrell as presenÈ a syntheÈic challenge. Fur Ehermore, 1n vl-er¡ of the growlng lnterest 1n the wfde IO physiological act,lviÈy of many cage compounds , a more general and efficlent synthes 1s of lceane derfvatfves should be devlsed that would make them uore acces s ible l+ for s tudy than exfsting routes have allowed. Therefore the synEhetic s Èrategy should allor¡ the lntroducÈl-on of functlonality LnÈo more than one rfng of the lceane molecule so that a wlde range of derivat fves could be prepared. tI- Retrosynthet,lc analysls d of the lceane structure has t2 been summarlzed prevLously . Owing to the sixfold inversion axLs of symnetry Ín the molecule, there are only tl'o types of carbon-carbon bonds present.. The analysis 1s thereby slnpllfted conslderably and a ffnal constructfon of the tceane skeleton Èhat lnvolves the formatlon of a s lngle bond ls 1tmlÈed t,o one of the two clas s es of subs tructures (7) or (8) . (7) (8) 5 Of these two posstbilltfes, substructure (7) appears more synthetically accesslble than substructure (8) sLnce, as O has been envLsaged befo..u , Èhe correct orient.aElon of the two three-carbon bridges fn the lat ter rutght be dlfficulE Èo assemble. An analys is of the subs tructure (7) suggests that a II synthon for rlng closure would be an Lntramolecular alkylaElon 13 of the ketone (9) provlded the ruethylene carbon bearing a leaving group X has the endo- conflguraÈlon as shown. o X (e) (10) lt{ IÈ is generally accepted thar the synthesf.s of a symmetrlcal molecule ls norrnally bes E accomplished from precursors havlng the same synmeÈry elements comparably located. Thts pract,lce facllitates the interpretatLon of spectra, ln partlcular NMR spectra, and frequently leads to a more dlrect and conceptually s1'npler synLhesls than might otherwlse be the case. I.¡1th thls fn mind and by Èhe applfcaElon of a synthon slmllar to chat, suggesEed for the preparaÈlon of compound (lO), the ketone (9) mlght lEself 6 be derived from the lntranolecular alkylation of elEher of Èhe compound Èypes (11) or (12). Further.., examination of the problems as socf ated wi th the che¡nis t ry of the o o X X X H (11) (11) o H.. hl X X t{- H- X X ri H o (r2) ( r2) ke t one (11) has already been dlscussed at. l+ d T2 length ' whereas work lnvolvlng the preparation of Ehe t5 diketone (12) is comparatively recenE and warranËs furÈher LnvestfgaÈ1on.
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