?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%2F20815%2F&rft.title=Endeavors+in+Methodology+Development+and+Natural+Product+Total+Synthesis&rft.creator=Li%2C+Xiben&rft.description=This+thesis+deals+with+the+development+of+new+reaction+methodology%2C+as+well+as+total+synthesis+of+natural+products.%0D%0AChapter+1+describes+readily+available+rhodium(II)+salts+catalyzed+B-H+insertion+reactions+between+NHC-boranes+(NHC-BH3)+and+diazocarbonyl+compounds+(N2CR1COR2).+Stable+%CE%B1-NHC-boryl+carbonyl+compounds+(NHC-BH2-CHR1COR2)+are+isolated+in+good+yields.+The+reaction+is+a+reliable+way+to+make+boron-carbon+bonds+with+good+tolerance+for+variation+in+both+the+NHC-borane+and+diazocarbonyl+components.+It+presumably+occurs+by+insertion+of+a+transient+rhodium+carbene+into+a+boron-hydrogen+bond+of+the+NHC-borane.+Competition+experiments+show+that+a+typical+NHC-borane+is+highly+reactive+toward+rhodium+carbenes.%0D%0AChapter+2+describes+the+synthetic+routes+towards+the+synthesis+of+tulearin+A+and+tulearin+C.+Large+scale+synthesis+of+the+bottom+fragments+(C1-C12)+and+the+top+fragment+(C13-C26)+for+tulearin+A+was+accomplished.+Different+synthetic+routes+were+tested+to+accomplish+the+total+synthesis+of+tulearin+A.+Some+major+problems+toward+the+total+synthesis+of+tulearin+A+were+identified+and+solved.+Meanwhile+a+novel+synthetic+route+towards+the+total+synthesis+of+tulearin+C+was+developed.+New+methodologies+were+applied+to+make+the+synthesis+more+efficient.+The+total+synthesis+of+tulearin+C+was+not+accomplished+because+of+the+difficulty+of+removal+of+the+acetate+protecting+group+at+C17.&rft.date=2014-05-29&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%2F20815%2F1%2FXiben_Li_PhD_Dissertation_2014.pdf&rft.identifier=++Li%2C+Xiben++(2014)+Endeavors+in+Methodology+Development+and+Natural+Product+Total+Synthesis.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++