?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%2F6354%2F&rft.title=GENERALIZATION+OF+HIGHLY+%C3%A3-REGIOSELECTIVE+SUBSTITUTIONS+IN+ALLYL+HALIDES+BY+ALKYLZINCS+AND+APPLICATIONS+TO+ZINC-ENE+CYCLIZATIONS+AND+THE+SYNTHESIS+OF+(R)-(%2B)-DIHYDRO-ALPHA-IONONE.&rft.creator=Ivanov%2C+Roman+Aleksandrovich&rft.description=Allyl+phenyl+sulfides+have+proven+to+be+extremely+versatile+and+widely+used+reagents+in+organic+chemistry.+There+are+thousands+of+publications+that+relate+their+uses+in+synthesis.+However%2C+the+conventional+method+of+preparing+%C3%A3-substituted+allyl+phenyl+sulfides+by+alkylation+of+deprotonated+commercially+available+allyl+phenyl+sulfides%2C+only+allows+electrophilic+groups+to+be+introduced.+This+method+fails+if+the+alkylating+agent+is+tertiary%2C+secondary%2C+vinylic%2C+or+arylic.+In+this+work+a+new+method%2C+in+which+a+nucleophilic+group+can+be+introduced+at+the+carbon+atom+bearing+the+phenylthio+group%2C+referred+to+as+%C3%A3-allylic+substitution%2C+is+thoroughly+studied+and+used+in+several+examples+to+demonstrate+its+significance+for+synthesis.+This+procedure+should+vastly+increase+access+to+a+wide+variety+of+allyl+phenyl+sulfides.+In+this+work%2C+copper+mediated+%C3%A3-allylic+substitution+reactions+of+organozinc+reagents+with+allyl+chlorides+bearing+a+%C3%A3-phenylthio+group+are+reported+and+the+best+reaction+conditions+for+mono-+and+dialkylzincs+are+revealed.+The+scope+and+limitations+of+%C3%A3-allylic+substitutions+of+organozincs+with+a+variety+of+different+allyl+chlorides+were+thoroughly+investigated+and+an+important+temperature+effect+was+observed+and+used+to+expand+the+scope+of+these+reactions.Furthermore%2C+this+work+deals+with+an+important+aspect+of+the+preparation+of+the+organometallic+nucleophiles+required+for+these+%C3%A3-substitutions.+Many+of+these+can+be+prepared+by+reductive+lithiation+of+readily+available+alkyl+phenyl+thioethers+by+aromatic+radical-anions.+However%2C+large-scale+preparations+suffer+from+the+requirement+of+separation+of+the+desired+product+from+the+aromatic+byproduct+using+either+slow+column+chromatography+or+vacuum+sublimation.+An+improved+procedure+for+reductive+lithiation+of+phenyl+thioethers+with+1-(N%2CN-dimethylamino)naphthalenide+was+developed+to+overcome+this+drawback.+Reductive+lithiation+was+then+used+not+only+as+a+preliminary+step+in+the+preparation+of+organozincs+for+copper+mediated+%C3%A3-regioselective+substitution+reactions+but+also+as+a+key+step+in+the+enantioselective+synthesis+of+(R)-(%2B)-dihydro-%C3%A1-ionone.+It+was+demonstrated+that+the+combination+of+reductive+lithiations%2C+zinc-ene+reactions+and+copper+mediated+organozinc+%C3%A3-regioselective+substitutions+can+be+used+for+efficient+syntheses+of+ring-fused+intermediates+in+an+iterative+and+stereoselective+fashion+from+inexpensive+commercially+available+starting+compounds&rft.date=2008-06-12&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%2F6354%2F1%2Froman_ivanov_2008_etd_v3.pdf&rft.identifier=++Ivanov%2C+Roman+Aleksandrovich++(2008)+GENERALIZATION+OF+HIGHLY+%C3%A3-REGIOSELECTIVE+SUBSTITUTIONS+IN+ALLYL+HALIDES+BY+ALKYLZINCS+AND+APPLICATIONS+TO+ZINC-ENE+CYCLIZATIONS+AND+THE+SYNTHESIS+OF+(R)-(%2B)-DIHYDRO-ALPHA-IONONE.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++