?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%2F6614%2F&rft.title=Synthetic+Methods+in+Organic+and+Supramolecular+Chemistry&rft.creator=Scott%2C+Colleen+Nicola&rft.description=The+synthesis+of+cyclophane+17+(9%2C10%2C11%2C12%2C26%2C27%2C28%2C29-octahydro-3H%2C8H%2C16H%2C20H%2C25H%2C+33H-4%2C7%3A21%2C24-+dimetheno+-13%2C19%2C15%3A30%2C2%2C32-di%5B1%5Dpropane%5B1%5Dyl%5B3%5Dylidine-1H%2C18H-dipyrimidino%5B1%2C2-a%3B1'%2C6'-o%5D+%5B1%2C8%2C15%2C22%5Dtetraazacyclo-+octacosine)+is+described.+Both+isomers+of+cyclophane+17+were+synthesized+over+nine+steps+in+46+%25+overall+yield+from+readily+available+starting+materials.+We+designed+and+synthesized+a+side+group+for+attachment+to+cyclophane+17%2C+which+we+wish+to+use+for+the+directed-complexation+of+the+cyclophane+with+a+specified+aromatic+guest.+We+had+hoped+to+use+the+Buchwald-Hartwig+reaction+to+attach+this+side+arm+to+the+secondary+amines+of+17%2C+but+despite+our+many+efforts+we+were+unable+to+achieve+this+goal+in+a+reproducible+manner.+We+have+developed+a+method+which+allows+the+stepwise+construction+of+silyl+ketals%3B+silyl+ketals+may+be+used+as+reactive+intermediates+in+the+construction+of+complex+molecules.+We+synthesized+silyl+ketals+3a+-+3i%2C+5a+-+5f+and+7a+-+7e+in+moderate+to+high+yields+using+a+combination+of+Rh2(OAc)4+followed+by+10+%25+Pd%2FC+or+Mn(CO)5Br+as+catalysts.+We+have+shown+that+diisopropylsilane+was+crucial+to+the+success+of+this+process+and+that+employing+(%2B)-ethyl+lactate+as+the+alcohol+in+the+first+step+leads+to+a+faster+and+more+efficient+reaction+in+the+second+step.+Silyl+ketals+7a%2C+7b+and+7d+were+used+to+show+that+intramolecular+radical+translocation+beyond+the+1%2C5+atom+was+not+only+feasible%2C+but+efficient.&rft.date=2005-06-06&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%2F6614%2F1%2Fcnscott_edt2005.pdf&rft.identifier=++Scott%2C+Colleen+Nicola++(2005)+Synthetic+Methods+in+Organic+and+Supramolecular+Chemistry.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++