New Adventures in the Synthesis of Hetero-Bridgedsyn-Facially Fused Norbornadienes (“[n]Polynorbornadienes”) and Their Topological Diversity

Abstract

Molecular Scaffolds formed by the linking of bicyclo[2.2.1]heptane (norbornane) subunits by sharing a common C 2bridge have great appeal to the molecular architect since modelling studies have shown that the syn-facially fused members have a curved topology. Furthermore, this curvature can be modified by replacement of the methylene bridge by heteroatom bridges (O, S, NR), and made rod-like by introducing a σ-bond between adjoining methylene bridges in sesquinorbornane subunits. This review presents synthetic methodology which allows the stereocontrolled construction [a] ). His research interests have focused on synthetic methodology involving cycloaddition chemistry (isobenzo systems) and photochemistry (small ring synthesis), with occasional forays into natural product synthesis (daunomycin, nucleosides, protoberberine). At the ANU, he set up a Centre for Forensic Science specialising in fingerprint detection, and has been the driving force behind the creation of the Centre for Molecular Architecture at CQU. He has published more than 250 research papers and was awarded a senior ARC Research Fellowship (1992Ϫ1996) and the RACI Organic Medal in 1996.MICROREVIEWS: This feature introduces the readers to the authors' research through a concise overview of the selected topic. Reference to important work from others in the field is included.

Neighbouring Group Participation in N-Methoxymethyl 7-Azanorbornanes 1: The Synthesis of N,N′-Methano-bridged Diazasesquinorbornanes, N3-[3]Polynorbornanes and CN3-[4]Polynorbornanes

“…Such scaffolds can be used to modify topology since molecular modelling shows that they are less curved than the compounds lacking the N,N-methanobridge. 11 The N-bridges are locked into a geometry corresponding to the highly disfavoured syn,syn-invertomer geometry of diazasesquinorbornanes, a feature which can be exploited in the molecular design of polarofacial scaffolds. The neighbouring group participation route is not restricted to N-C-N bridges and other examples will be reported in due course.…”

Synthesis and Characterization of Biologically Potent Chalcone Bearing 1,3,4-Oxadiazole Linkage

“…1,3,4-oxadiazole is commonly utilized pharmacophore has been subjected to extensive study in the recent years due to their metabolic profile and ability to engage in hydrogen bonding with receptor site. 1,3,4-Oxadiazoles are an important class of heterocyclic compounds with a wide range of biological activities such as antiviral [10], antimicrobial [11], antineoplastic [12], fungicidal [13], anticancer [14,15], inhibition of tyrosinase [16], They are also useful intermediates in organic synthesis [17] and widely employed as electron transporting and hole-blocking materials.…”

Dipolar Cycloaddition Reactions of Azomethine Ylides Generated by endocyclic‐exocyclic 1,3‐dipole Rearrangement

“…The polynorbornanes (such as 4 , Scheme ) are under research for use in nanotechnology, energy, and electron transfer, as anticancer bis‐intercalators and self‐assembled systems . Other possibilities for their use exist in the production of new materials and host/guest chemistry.…”

“…Diels–Alder (DA) reactions were the main way used to make polynorbornanes until the discovery of “Alkene Cyclobuane Epoxide (ACE)‐couplingˮ and its nitrogen counterpart “aza ACE‐coupling.ˮ DA approach was successful in producing various sesquinorbornanes but limited in producing larger polynorbornanes . The main drawback in using DA cycloadditions to produce polynorbornanes was that the reaction exhibited little stereocontrol.…”