?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%2F9594%2F&rft.title=The+Development+of+an+Electron+Transfer+Initiated+Cyclization+Approach+Toward+the+Total+Synthesis+of+Mycalamide+B.+The+Synthesis+of+the+N7-C25+Fragment+of+Psymberin&rft.creator=Rech%2C+Jason+Christopher&rft.description=The+electron+transfer+initiated+cyclization+(ETIC)+has+been+shown+to+be+an+efficient+method+for+the+generation+of+cyclic+amido+acetals.+The+tetrahydrofuranyloxy+methyl+ether+was+shown+to+be+a+stable+nucleophilic+hemiacetal+surrogate+allowing+for+the+incorporation+of+a+formaldehyde+equivalent+in+the+ETIC+reaction.+The+ETIC+reaction+was+employed+in+the+stereoselective+synthesis+of+amido+trioxadecalin+systems+relevant+to+the+synthesis+of+the+mycalamides%2C+onnamides+and+theopederins.+The+stereoselectivity+resulting+from+these+cyclizations+was+controlled+by+the+substituents+of+the+tetrahydropyran+ring+and+the+conformational+bias+of+the+developing+trioxadecalin+system.+The+epimerization+of+the+N-acylaminal+center+of+the+amido+trioxadecalin+system+was+possible+under+mildly+acidic+conditions.+An+efficient+and+stereoselective+synthetic+route+has+been+developed+that+intends+to+employ+the+ETIC+reaction+to+selectively+generate+the+N-acylaminal+of+mycalamide+B.+A+linear+approach+to+the+generation+of+the+right+half+of+mycalamide+B+has+been+applied+allowing+for+expedient+access+to+the+dimethyl+tetrahydropyran+core.+The+synthetic+sequence+employs+an+asymmetric+Leighton+allylation%2C+selective+boron+mediated+aldol%2C+1%2C3-syn-reduction%2C+and+selective+epoxidation+and+syn-vinylation+to+establish+the+stereochemistry+of+the+right+hand+fragment+of+mycalamide+B.+The+stereoselective+synthesis+of+the+N7-C24+fragment+of+psymberin+was+developed.+The+synthesis+is+highlighted+by+the+de+novo+generation+of+the+C25-C17+pentasubstituted+arene+that+allows+for+the+expedient+generation+of+multigram+quantities+of+this+intermediate.+The+stereochemistry+of+this+fragment+was+established+by+an+asymmetric+Brown+crotylation+and+Leighton+allylation%2C+selective+Mukaiyama+aldol+addition%2C+1%2C3-syn-reduction%2C+and+a+selective+Lewis+acid+catalyzed+TMSCN+displacement+of+an+acyl+lactol.&rft.date=2006-03-20&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%2F9594%2F1%2Frechjc05.pdf&rft.identifier=++Rech%2C+Jason+Christopher++(2006)+The+Development+of+an+Electron+Transfer+Initiated+Cyclization+Approach+Toward+the+Total+Synthesis+of+Mycalamide+B.+The+Synthesis+of+the+N7-C25+Fragment+of+Psymberin.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++