?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%2F9310%2F&rft.title=SYNTHETIC+EFFORTS+TOWARDS+INGENOL+CROSS-CONJUGATED+TRIENES+AND+THEIR+APPLICATION+TO+RAPID+INCREASES+IN+MOLECULAR+COMPLEXITY&rft.creator=You%2C+Lingfeng&rft.description=Synthesis+of+the+ingenol+skeleton+using+a+Pauson-Khand+reaction+as+the+key+step+was+investigated.+Although+the+Pauson-Khand+reaction+failed+to+provide+the+highly+strained+ingenol+skeleton%2C+several+relatively+complex+Pauson-Khand+precursors+were+prepared+in+about+ten+steps.+The+scope+and+limitation+of+the+Pauson-Khand+reaction+in+accessing+highly+strained+molecules+were+studied.+A+rhodium(I)-catalyzed+allenic+Alder-ene+reaction+was+developed+that+provides+cross-conjugated+trienes+in+good+yields.+This+method+shows+enticing+functional+group+compatibility%2C+and+progress+has+been+made+to+increase+the+stereoselectivity+of+the+olefinic+side+chain+via+iridium(I)+catalysis.+A+consecutive+one-pot+Alder-ene%2F%5B4%2B2%5D%2F%5B4%2B2%5D+reaction+has+been+developed+to+demonstrate+the+potential+of+the+cross-conjugated+triene+for+accessing+polycyclic+compounds.+The+reaction+sequence+is+highly+selective+with+the+Alder-ene+and+the+first+Diels-Alder+reaction+only+providing+a+single+isomer+and+the+intermolecular+%5B4%2B2%5D+cycloaddition+giving+two+endo+addition+products+resulting+from+addition+of+the+dienophile+to+either+face+of+the+diene.+The+transformation+is+highly+atom-efficient+with+all+the+atoms+of+the+starting+dialkynyl+allenes+and+the+dienophiles+appearing+in+the+products.&rft.date=2006-03-30&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%2F9310%2F1%2FLingfengYou.pdf&rft.identifier=++You%2C+Lingfeng++(2006)+SYNTHETIC+EFFORTS+TOWARDS+INGENOL+CROSS-CONJUGATED+TRIENES+AND+THEIR+APPLICATION+TO+RAPID+INCREASES+IN+MOLECULAR+COMPLEXITY.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++