The primary aim of this project was to synthesize new heterocyclic dimers of isoflavones and flavones, and investigate various methodologies for their synthesis. The secondary aim of the project was to synthesize some flavonoid natural products. Dimeric systems were synthesized using various methodologies including acid catalyzed arylation of isoflavanols and flavanols, acid catalyzed dimerization of flavenes, oxidative dimerization, Sonogashira coupling, Ullmann coupling and Suzuki-Miyaura coupling reactions. The acid catalyzed arylation of isoflavanols was found to proceed in a very stereoselective fashion to give trans-4-arylisoflavans in good yield in a single step. However, related flavanols under similar conditions gave mixtures of cis and trans isomers of 4-arylflavans. Interestingly, it was found that appropriately substituted flavenes, upon treatment with acid undergo stereoselective rearrangement and dimerization to give benzopyranobenzopyrans in high yields. A rationale for the rearrangement is proposed and this dimerization was used for the stereoselective synthesis of the natural product dependensin. As part of the project, some polycyclic natural products such as octandrenolone, flemiculosin, 3-deoxy-MS-II and laxichalcone were also synthesized. Oxidative dimerization of activated isoflavones was found to be very regioselective, and novel isoflavone dimeric systems were synthesized. Related flavones however, failed to undergo dimerization under similar conditions. A probable explanation for high regioselectivity in the case of isoflavones and unreactivity of flavones has been presented. Phenol oxidative coupling was used for the one-step synthesis of another natural product kudzuisoflavone-A from daidzein. Sonogashira coupling was utilized for the synthesis of dimeric systems linked via an acetylic linker. A variety of soflavone isoflavone, flavone-flavone and isoflavone-flavone dimers were synthesized in "one-pot" by this methodology and in excellent yields. Although Ullmann coupling was found not to be suitable for the synthesis of isoflavone or flavone dimers, one-pot Suzuki-Miyaura methodology gave flavone dimers and various other heterocyclic dimers in good yields.

Novel indolo-macrocycles have been generated from the attempts to synthesise bis-indolo-cyclotriveratrylenes by the condensation of I, I'-diindolyl-3,3'-dimethanols catalysed by p-toluenesulfonic acid. The addition of substituents on indoles led to enhanced solubilities of the macrocycles. Nine- and six-membered ring compounds have been synthesized from the acid-catalysed reaction of I,I'-diindolyl compounds and aryl aldehydes. Some reactions of these compounds and the attempted synthesis of 2,2' diindolylmethanes from the cyclic compounds have also been described. The electrophilic substitution reactions of 3-substituted 4,6-dimethoxyindole 2,6-dimethanols and 3-substituted 4,6-dimethoxyindole-7 and 2-carbaldehydes and I-substituted indoles afforded triindolyl dialdehydes. The wriation of substituents at C-7 of indole-7-aldehydes and at C-2 of indole-2-aldehydes has also been discussed. Reaction of the hydroxymethylindole and 1,2-di(indol-I-ylmethyl)benzene gave a new macrocycle. Substitution reactions of 2,2???-diindolylmethane-7,7'-dimethanol and indole-7- and 2-aldehydes gave tetraindolyl dialdehydes. Sodium borohydride reduction of tri- and tetra-indolyl dialdehydes gave tri- and tetra-indolyl dimethanols respectively. Acid-catalysed reactions of tri- and tetra-indolyl dimethanols afforded only calix[3] and [4]indoles respectively when all substituents at C-3 of indoles were aryl groups. New conditions for indole based imine synthesis have been established Macrocyclic imine formation from mono-, di-, tri and tetra-indolyl dialdehydes has been investigated. Reactions of indole-3, 7-dialdehydes and short chain diamines (1,2-diaminoethane, 1,2-diaminobenzene and 1,6-diaminohexane) gave mixtures while the reactions with long chain diamines (1,10 diaminodecane and 1,12-diaminododecane) gave monoindolyl macrocyclic imines. Reaction of indole-2, 7-dialdehydes and short chain diamines afforded diindolyl macrocyclic imines with head-tail structures, and the 2,7';2',2";7",2'''-Tetraindole-7 ,7"'-dialdehyde underwent cyclisation with triindolyl dialdehydes and 1,6-diaminohexane afforded triindolyl macrocyclic imines. 1,2 diaminoethane while the 2,3 ';1',1 ";3 ",2"'-tetraindole-7,7"'-dialdehydes underwent imine, with its precise structure established by X-ray crystallography. Reaction of of 1,3-di(indol-l-ylmethyl)benzene and 1,2 diaminoethane yielded a new macrocyclic reactions with long chain diamines yielded monoindolyl macrocyclic imines. Reaction ring closure with 1,2 diaminoethane and 1,6-diaminohexane.

Diss. (sammanfattning) Uppsala : Uppsala universitet, 2005. / Härtill 4 uppsatser.

Thesis (Ph.D.) -- University of Adelaide, Department of Organic Chemistry, 1981.

Thesis (Ph.D.) -- University of Western Sydney, 2003. / "A thesis submitted in partial fulfilment of the requirements of the degree of Doctor of Philosophy , University of Western Sydney, Campbelltown, February 2003". Includes references : leaves 188 - 200, and appendices.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--Northeastern University, 2008. / Title from title page (viewed March 9, 2009) Graduate School of Arts and Sciences, Dept. of Chemistry and Chemical Biology. Includes bibliographical references (p. 192-205).

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--Michigan State University. Dept. of Chemistry, 2006. / Title from PDF t.p. (viewed on Nov. 17, 2008) Includes bibliographical references. Also issued in print.

Thesis (Ph. D.)--West Virginia University, 2008. / Title from document title page. Document formatted into pages; contains xv, 275 p. : ill. Includes abstract. Includes bibliographical references (p. 107-113).