?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%2F8937%2F&rft.title=Asymmetric+Alkenyl+Zirconocene%2FZinc+Additions+to+Aldehydes+and+Synthetic+Efforts+Toward+Pseudotrienic+Acid+A&rft.creator=Jayasuriya%2C+Nilukshi+Renuka&rft.description=The+in+situ+hydrozirconation-transmetalation-aldehyde+addition+process+is+a+convenient+method+for+the+generation+of+allylic+alcohols.+Ongoing+research+has+focused+on+enhancing+the+enantioselectivity+and+substrate+scope+of+this+process+and+will+be+the+focus+of+Chapter+1.+Investigations+have+shown+that+both+amino+alcohols+and+amino+thiols+show+moderate+to+high+enantioselectivity.+Non-linear+effects+were+analyzed+in+order+to+gain+mechanistic+insight+into+the+asymmetric+addition+process.+Additionaly%2C+analogues+of+both+classes+of+ligands+have+been+synthesized+and+evaluated.+Amino+thiol+ligands+tend+to+show+the+highest+enantioselectivities+due+to+the+higher+affinity+of+sulfur+for+zinc+over+zirconium.+A+new+class+of+valine-based+ligands+was+identified+to+be+quite+effective%2C+in+terms+of+ligand+loading+and+%25+ee+in+the+formation+of+allylic+alcohols.+In+Chapter+2%2C+progess+toward+pseudotrienic+acid+A+is+discussed.+The+goal+of+this+project+was+the+synthesis+of+pseudotrienic+acid+A+utilizing+alkenylzirconium%2Fzinc+methodology+cultivated+in+the+Wipf+group+and+to+elucidate+the+absolute+configuration+at+C(20)+of+the+target+molecule.+A+brief+summary+of+the+only+reported+synthesis+of+pseudotrienic+acid+B+by+Cossy+et+al.+is+outlined%2C+followed+by+the+retrosynthetic+plan+and+synthesis+of+the+3+main+fragments+of+this+molecule.+Lastly%2C+the+current+progress+towards+the+coupling+of+these+fragments+is+examined.&rft.date=2007-09-20&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%2F8937%2F1%2FJayasuriyan_2007etdpitt.pdf&rft.identifier=++Jayasuriya%2C+Nilukshi+Renuka++(2007)+Asymmetric+Alkenyl+Zirconocene%2FZinc+Additions+to+Aldehydes+and+Synthetic+Efforts+Toward+Pseudotrienic+Acid+A.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++