?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F7053%2F&rft.title=Homolytic+Aromatic+Substitution%2C+Conformational+Dynamics+of+Dihydrophenanthridines%2C+and+High-Throughput+Synthesis+of+Amides+with+Fluorous+Technology%3A+Methodologies+in+Reaction%2C+Analysis%2C+and+Separation&rft.creator=Keller%2C+Adam+I.&rft.description=Homolytic+aromatic+substitution+encompasses+a+wide+range+of+synthetic+transformations+based+on+inter-+and+intramolecular+additions+of+radicals+to+arenes.+Additions+of+radicals+derived+from+aryl+iodides+to+arenes+are+promoted+by+tris(trimethylsilyl)silane+and+occur+under+exceptionally+mild+conditions+in+non-degassed+benzene.+Experimental+observations+led+to+a+proposed+mechanism+involving+reaction+of+the+intermediate+cyclohexadienyl+radical+with+dioxygen+to+generate+the+aromatic+product+and+the+hydroperoxy+radical.+This+methodology+was+extended+to+the+synthesis+of+biaryl+and+heterocyclic+compounds.N-Acetyldihydrophenanthridines+exhibit+remarkable+conformational+dynamics+that+are+observable+on+the+NMR+timescale.+Semiempirical+calculations+were+performed+to+understand+their+conformational+preferences.+The+predictions+derived+from+the+calculated+structures+were+verified+by+x-ray+crystallography%2C+two-dimensional+exchange+and+variable+temperature+NMR+spectroscopy.+The+rate+constants+for+conformational+switching+were+calculated+by+a+matrix-based+routine+with+data+extracted+from+the+two-dimensional+exchange+spectra.A+fluorous+equivalent+of+diisopropylcarbodiimide+(FDIC)+was+synthesized+to+overcome+the+separation+problems+encountered+when+conducting+solution-phase%2C+carbodiimide+mediated+acyl+couplings.+The+reactivity+of+the+fluorous+analog+was+not+greatly+affected+by+the+presence+of+a+fluorous+domain%2C+and+was+equally+as+effective+as+diisopropylcarbodiimide+in+facilitating+amide+bond+formation.+Coupled+with+a+reverse+F-SPE+strategy%2C+FDIC+mediated+couplings+were+conducted+to+provide+the+target+amides+in+high-purities+(95-99%25).+A+small+library+of+amides+was+prepared+in+a+high-throughput+fashion+to+demonstrate+the+utility+of+this+approach.&rft.date=2007-06-21&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F7053%2F1%2FKellerAI.pdf&rft.identifier=++Keller%2C+Adam+I.++(2007)+Homolytic+Aromatic+Substitution%2C+Conformational+Dynamics+of+Dihydrophenanthridines%2C+and+High-Throughput+Synthesis+of+Amides+with+Fluorous+Technology%3A+Methodologies+in+Reaction%2C+Analysis%2C+and+Separation.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++