?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%2F9769%2F&rft.title=Applications+of+Iridium-Catalyzed+Isomerization+Claisen+Rearrangements+(ICR)+to+Complex+Molecule+Synthesis&rft.creator=Stevens%2C+Benjamin+Dawson&rft.description=The+iridium-catalyzed+isomerization+Claisen+rearrangement+(ICR)+methodology+developed+in+theNelson+group+has+provided+access+to+a+broad+range+of+diastereomerically+enricheddisubstituted+unsaturated+aldehydes.+Allylsilyl+aldehydes+produced+by+the+ICR+reaction+havebeen+further+elaborated+into+substrates+for+highly+diastereoselective+intramolecular+Hosomi-Sakurai+annulation+reactions.+The+Sakurai+annulation+has+proven+to+be+particularly+powerfulwhen+carried+out+in+tandem+with+intramolecular+aldol+or+Mannich+reactions+to+form+complexfused+ring+systems.+An+attempted+strategic+application+of+this+methodology+to+the+synthesis+ofthe+Rauwolfia+alkaloids+reserpine+and+yohimbine+is+detailed.Vinyl+boronic+esters+have+been+demonstrated+to+be+effective+precursors+for+the+ICRreaction+providing+diastereomerically+enriched+boronic+aldehydes.+The+potential+forintramolecular+chelation+between+the+newly+formed+aldehyde+and+proximal+boronic+ester+hasbeen+investigated.+The+boron+functionality+has+proven+to+be+useful+for+accessing+alkoxy-+andaryl-substituted+compounds+that+are+typically+unavailable+from+the+ICR+reaction.+A+synthesis+ofthe+plant+growth+inhibitor+penieone+has+been+explored+in+order+to+demonstrate+the+practicalapplication+of+this+methodology+to+complex+molecule+construction.&rft.date=2007-09-19&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%2F9769%2F1%2FBDStevensETD.pdf&rft.identifier=++Stevens%2C+Benjamin+Dawson++(2007)+Applications+of+Iridium-Catalyzed+Isomerization+Claisen+Rearrangements+(ICR)+to+Complex+Molecule+Synthesis.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++