?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%2F8877%2F&rft.title=A+Stereochemical+Comparison+Between+Radical+Atom+Transfer+Cyclizations+and+Organozinc+Cyclizations+of+Primary+and+Secondary+Hexenyl+Iodides&rft.creator=Gibney%2C+Heather+Marie&rft.description=Cyclized+hexenylzinc+iodides+have+been+reported+to+give+different+cis%3Atrans+product+ratios+than+the+analogous+radical+cyclized+hexenyl+iodides+and+this+has+been+taken+as+evidence+that+the+organozinc+and+not+radical+cyclizations+are+involved.+Unfortunately%2C+temperature+dependence+was+not+taken+into+account+when+comparing+the+two+sets+of+ratios.+To+further+investigate+these+differing+cis%3Atrans+ratios%2C+three+hexenyl+iodides+were+synthesized+and+cyclized+under+radical+atom+transfer+conditions+between+5+%C2%B0C+and+80+%C2%B0C.+The+resulting+cis%3Atrans+product+ratios+were+measured+by+gas+chromatography.+The+cis%3Atrans+ratios+observed+ranged+from+high+(i.e.+cis%3Atrans+1%3A13.3)+to+low+(cis%3Atrans+2.0%3A1)%3B+the+selectivities+decreased+as+the+temperature+increased.+Comparison+of+cis%3Atrans+ratios+of+the+products+from+the+zinc+cyclization+to+the+cis%3Atrans+ratios+of+the+products+from+the+radical+cyclizations+at+the+same+temperatures+showed+that+the+two+sets+of+ratios+were+within+experimental+error+of+each+other.+It+was+concluded+that+the+zinc+mediated+cyclizations+of+primary+and+secondary+alkenyl+iodides+to+give+cyclopentylmethylzinc+halides+involve+radical+cyclizations.&rft.date=2006-09-28&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%2F8877%2F1%2Fgibneyhm2006.pdf&rft.identifier=++Gibney%2C+Heather+Marie++(2006)+A+Stereochemical+Comparison+Between+Radical+Atom+Transfer+Cyclizations+and+Organozinc+Cyclizations+of+Primary+and+Secondary+Hexenyl+Iodides.++Master's+Thesis%2C+University+of+Pittsburgh.++++(Unpublished)++