?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%2F9166%2F&rft.title=Mechanistic+and+Stereochemical+Studies+of+Photoinduced+Electron+Transfer+Initiated+Cyclization+Reactions%3A+The+Role+of+Nitrogen.+The+Aqueous+Prins+Reaction+and+Efforts+Towards+the+Total+Synthesis+of+(%2B)-Dactylolide&rft.creator=Aubele%2C+Danielle+L.&rft.description=A+novel+method+for+catalytic+electron+transfer+initiated+cyclization+reaction+for+the+formation+of+cyclic+acyl+aminals+through+a+unique+method+of+carbon-carbon+%C3%B3-bond+activation+has+been+developed.+This+new+cyclization+strategy+employs+a+potent+electrophile%2C+generated+by+a+photoinitiated+single+electron+oxidation+of+a+homobenzylic+amide+or+t-butyl+carbamate%2C+which+reacts+with+an+appended+nucleophile+allowing+for+the+formation+of+cyclic+acyl+aminals.+The+Lewis+acid-surfactant-combined+catalyst+(LASC)+was+employed+in+a+novel+method+for+effecting+intramolecular+Prins+cyclization+reactions+in+water.+Acetals+of+1%2C2+and+1%2C3+di-+and+tri-+substituted+alcohols+with+a+tethered+allyl+silane+have+been+converted+to+2%2C6-syn-tetrahydropyrans.+The+LASCs+are+generated+in+situ+by+the+addition+of+cerium+nitrate+to+a+solution+of+sodium+dodecylsulfate+and+acetal+in+water.+A+heterogeneous+reaction+environment+is+created+in+which+the+acetal+is+trapped+within+the+hydrophobic+core+of+the+immediately+generated+micelle.+Intarmolecular+Prins+cyclization+is+catalyzed+upon+interaction+of+the+acetal+with+Lewis+acidic+cerium+cations+located+at+the+surface+of+the+micelle.+LASC+mediated+intramolecular+Prins+cyclization+reactions+are+efficient%2C+high+yielding%2C+and+an+environmentally+benign+method+of+generating+2%2C6-cis-tetrahydropyrans.+A+highly+convergent+route+towards+the+total+synthesis+of+the+marine+macrolide+(%2B)-dactylolide+is+currently+being+pursued.+The+route+involves+the+condensation+of+two+highly+functionalized+segments+of+the+molecule%2C+an+%C3%A1%2C%C3%A2-unsaturated+aldehyde+and+a+1%2C3-syn-diol%2C+to+form+a+cyclic+%C3%A1%2C%C3%A2-unsaturated+acetal.+Both+enantiopure+segments+arise+from+vinylogous+aldol+reactions%2C+providing+the+three+necessary+stereocenters.+The+key+synthetic+transformation+involves+intramolecular+Prins+cyclization+of+a+cyclic+%C3%A1%2C%C3%A2-unsaturated+acetal+with+a+pendent+allylsilane+to+provide+the+2%2C6-cis-disubstituted-4-methylenetetrahydropyran+core+of+the+molecule+efficiently+and+stereoselectively.+Other+key+transformations+include+a+completely+trans+selective+selenoxide-selenate+%5B2%2C3%5D+sigmatropic+rearrangement+and+the+selective+oxidation+of+a+primary+allylic+alcohol+in+the+presence+of+a+secondary+alcohol+with+Dess-Martin+periodinane.&rft.date=2004-09-22&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%2F9166%2F1%2Faubele8182004.pdf&rft.identifier=++Aubele%2C+Danielle+L.++(2004)+Mechanistic+and+Stereochemical+Studies+of+Photoinduced+Electron+Transfer+Initiated+Cyclization+Reactions%3A+The+Role+of+Nitrogen.+The+Aqueous+Prins+Reaction+and+Efforts+Towards+the+Total+Synthesis+of+(%2B)-Dactylolide.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++