Selective distal functionalization of resorcinarenes via an ortholithiation approach

Thesis (MSc)--Stellenbosch University, 2012.ENGLISH ABSTRACT: Resorcinarenes are tetramers, belonging to a class of [1]4metacyclophanes, easily formed by the acid- or base-catalysed condensation of resorcinol and aldehydes. Properties include, amongst others; bowl-like shape, adhesion to hydrophilic surfaces and formation of hexameric capsules. Their uses are, to mention some: components in liquid crystals, photoresistors, selective membranes, surface reforming agents, HPLC stationary phases, ion-channel mimics, metal-ion extraction, molecular switches and ligands for metal catalysts. Selective functionalization of resorcinarenes has been explored and achieved via relatively inefficient methodologies which limit studies, structural architecture and new applications. In this work, synthesis of C4v symmetric resorcinarene ethers was performed which were used as templates in undertaking studies towards selective derivatisation of resorcinarenes via an ortholithiation approach. Conditions for the efficient synthesis of distally substituted resorcinarenes using ortholithiation were optimized and tested with a range of electrophiles, lower rim lengths, scale, base equivalents, reaction times and solvent effects. Ortholithiation gave distally substituted resorcinarenes in reasonable yields (>80%). Ortholithiation and its ability to form distal-resorcinarene esters could possibly be used as a way to synthesize distal-chloromethyl resorcinarene precursors whose further functionalization would furnish a range of distal-resorcinarene imidazolium salts, a class of distal bidentate carbene ligand staring materials for transition metal coordination.AFRIKAANSE OPSOMMING: Resorsinarene is sikliese tetramere, wat deel uitmaak van 'n klas van [1]4metasiklofane, en kan maklik gevorm word deur die suur- of basis-gekataliseerde kondensasie van resorsinol en aldehiede. Eienskappe sluit onder andere in: bak-vormig, adhesie aan hidrofiliese oppervlakke en die vormasie van heksameriese kapsules. Tipiese voorbeelde van gebruike sluit die volgende in: komponente van vloeistof kristalle, fotoresistors, selektiewe membrane, oppervlak hervormings agente, HDVC stationêre fases, ioon-kanaal nabootsers, metaal-ioon ekstraksie, molekulêre skakelaars en ligande vir metaalkatalise. Selektiewe funksionalisering van resorsinarene was al voorheen bestudeer, maar die metodologieë was beperkend ten opsigte van die struktuele argitektuur en nuwe toepassings wat daaruit gekom het. In hierdie werk was C4v simmetriese resorsinareen eters gesintetiseer wat gebruik was as uitgangstowwe om selektiewe funksionalisering deur orto-litiëring te bewerkstellig. Kondisies vir die effektiewe sintese van distaal gesubstitueerde resorsinarene, deur gebruik te maak van orto-litiëring, was bepaal en ge-optimaliseer deur gebruik te maak van 'n wye reeks elektrofiele, laer rand lengtes, reaksieskale, basis ekwivalente en reaksie tye. Deur dié proses was dit moontlik om distaal gesubstitueerde resorsinareen produkte te bekom in redelike opbrengste (>80%) met meeste funksionele goepe. Daar word voorsien om orto-litiëring, en sy vermoë om distale-resorsinareen esters te vorm,van gebruik te maak as 'n beginpunt in die sintese van distale-chlorometiel resorsinarene, wat op hulle beurt weer sal dien as uitgangstowwe vir die sintese van distale-resorsinareen imidasolium soute. Hierdie distale, bidentale soute kan gebruik word as karbeen ligande in oorgangsmetaal koordinasie