?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%2F9739%2F&rft.title=An+Investigation+of+the+Pederin+Family%3A+Total+Synthesis+of+Theopederin+D%3B+Synthesis+and+Determination+of+the+Relative+and+Absolute+Configuration+of+Psymberic+Acid&rft.creator=Green%2C+Michael+E&rft.description=An+investigation+of+the+pederin+family+of+natural+products+has+led+to+the+total+synthesis+of+theopederin+D%2C+a+synthesis+of+the+C1-C6+portion+of+psymberin+(psymberic+acid)%2C+and+the+determination+of+the+absolute+configuration+of+C4+and+C5+of+this+fragment.Highlights+of+our+theopederin+D+synthesis+include+the+use+of+an+asymmetric+ketene-aldehyde+cycloaddition+to+synthesize+the+A+ring+(or+pederic+acid+subunit)%2C+a+1%2C5-anti-boron+mediated+aldol+to+construct+the+C16-C17+bond+with+high+a+high+level+of+diastereocontrol%2C+formation+of+the+C+and+D+rings+in+a+one-pot%2C+six+reaction+sequence%2C+selective+differentiation+of+a+tetrahydrofuranol+in+the+presence+of+a+tetrahydropyranol%2C+and+elaboration+of+the+C+ring+using+vinylation+chemistry+developed+by+Yamamoto+and+Rainier.The+stereochemically+labile+B+ring+of+theopederin+D+was+constructed+during+the+late+stages+of+this+synthesis+using+carbon-carbon+bond+activation+via+an+Electron+Transfer+Initiated+Cyclization+(ETIC)+method+previously+developed+in+the+Floreancig+research+laboratories.+This+transformation+proceeded+under+essentially+neutral+conditions+and+furnished+the+desired+amidotrioxadecalin+in+high+yield.+The+total+synthesis+of+theopederin+D+was+completed+through+coupling+of+pederic+acid+and+an+aminotrioxadecalin+fragment+using+a+modified+diastereoselective+strategy+initially+developed+by+Rawal.Our+efforts+toward+the+total+synthesis+of+psymberin+involved+the+synthesis+of+psymberic+acid%2C+as+its+absolute+and+relative+stereochemistry+was+previously+undefined.+The+use+of+readily+available+starting+materials+(D-+or+L-serine)+and+subsequent+elaboration+using+syn+or+anti+selective+methallylation+allowed+for+the+efficient+construction+of+all+possible+stereoisomers+of+psymberic+acid.+The+absolute+configuration+of+psymberic+acid+was+determined+through+natural+product+and+model+system+degradative+studies%2C+and+analysis+of+the+reaction+products+using+a+gas-chromatography%2F+mass+spectrometry+apparatus+(GC-MS)+outfitted+with+a+chiral+stationary+phase.&rft.date=2009-01-28&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%2F9739%2F1%2Fthesis_green_me_112708_corrected.pdf&rft.identifier=++Green%2C+Michael+E++(2009)+An+Investigation+of+the+Pederin+Family%3A+Total+Synthesis+of+Theopederin+D%3B+Synthesis+and+Determination+of+the+Relative+and+Absolute+Configuration+of+Psymberic+Acid.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++