?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%2F22757%2F&rft.title=A+Dehydrogenative+Dehydro-Diels-Alder+Reaction+and+its+Application+to+Fluorescent+Tools+and+Natural+Product+Synthesis&rft.creator=Kocsis%2C+Laura%2FS&rft.description=Functionalized+naphthalenes+are+valuable+building+blocks+in+many+areas+of+chemistry%2C+such+as+natural+products%2C+drugs%2C+and+fluorescent+dyes%2C+but+advances+in+new+synthetic+methods+to+generate+naphthalenes+have+been+limited.+We+have+developed+a+microwave-assisted%2C+intramolecular+dehydrogenative+dehydro-Diels%E2%80%93Alder+(DDDA)+reaction+of+styrenyl+derivatives+which+affords+cyclopenta%5Bb%5Dnaphthalene+products+that+cannot+be+accessed+using+existing+synthetic+strategies.+The+DDDA+reaction+can+be+performed+in+as+little+as+30+minutes+to+provide+diverse+naphthalene+compounds+exclusively+and+in+high+yields%3B+only+in+examples+involving+heteroatom+substitution+of+the+styrene-yne+tether+were+mixtures+of+naphthalene+and+dihydronaphthalene+products+obtained.%0D%0A+%0D%0AIn+order+to+better+understand+and+control+the+selectivity+of+DDDA+reactions+resulting+in+product+mixtures%2C+the+mechanisms+of+formation+for+the+naphthalene+and+dihydronaphthalene+substrates+were+investigated.+Isotopic+labeling+experiments+and+gas+detection+studies+revealed+that+these+two+products+were+generated+via+diverging+mechanisms+of+a+common+intermediate%2C+where+dihydronaphthalene+substrates+were+produced+via+a+radical+pathway%2C+while+naphthalene+compounds+were+yielded+by+unimolecular+elimination+of+hydrogen+gas.+As+an+additional+outcome+of+these+mechanistic+studies%2C+reaction+conditions+were+established+for+the+selective+production+of+either+naphthalene+or+dihydronaphthalene+products+in+high+yields.+%0D%0A%0D%0AThe+synthetic+utility+of+the+DDDA+reaction+was+demonstrated+by+its+application+to+the+synthesis+of+eight+aryldihydronaphthalene+and+arylnaphthalene+lignan+natural+products%2C+including+taiwanin+C+and+justicidin+B.+Computational+methods+for+chemical+shift+assignment+were+developed%2C+which+showed+good+correlation+with+experimental+spectra+and+allowed+for+regioisomeric+lignans+to+be+distinguished.+The+synthetic+utility+of+DDDA+reaction+was+also+realized+by+a+single-step+conversion+of+halogenated+cyclopenta%5Bb%5Dnaphthalene+substrates+to+solvatochromic+fluorophores.+These+fluorescent+dyes+displayed+red-shifted+spectral+properties+compared+to+PRODAN%2C+a+commonly+used+and+structurally+related+fluorescent+biological+probe%2C+making+them+potentially+valuable+for+study+in+biological+systems.+Moreover%2C+structure-photophysical+property+relationships+(SPPR)+of+cyclopenta%5Bb%5Dnaphthalene+dyes+were+determined+by+utilizing+the+DDDA+reaction+to+introduce+systematic+variations+in+fluorophore+structure%2C+such+as+changes+in+donor+position%2C+which+significantly+altered+the+dyes%E2%80%99+photophysical+properties.+The+SPPR+determined+will+allow+for+the+future+rational+design+and+tuning+of+fluorophore+structure+and+photophysical+properties+to+address+specific+needs+in+biological+applications.%0D%0A&rft.date=2015-01-13&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%2F22757%2F1%2FKocsis_Final_ETD_Document.pdf&rft.identifier=++Kocsis%2C+Laura%2FS++(2015)+A+Dehydrogenative+Dehydro-Diels-Alder+Reaction+and+its+Application+to+Fluorescent+Tools+and+Natural+Product+Synthesis.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++