Matches in SemOpenAlex for { <https://semopenalex.org/work/W2002156975> ?p ?o ?g. }
- W2002156975 endingPage "1744" @default.
- W2002156975 startingPage "1735" @default.
- W2002156975 abstract "In order to explore the effect of electron-withdrawing substituents on 2-norpinyl (bicyclo[3.1.1]hept-2-yl)→2-norbornyl (bicyclo[2.2.1]hept-2-yl) rearrangements, cyano and penta-fluoroethyl groups were introduced into the α and β (= bridgehead) positions. The substrates were synthesized from norpinan-2-one (8) by addition of HCN or C2F5Li, from 2-aminonorbornane-2-carbonitrile (25) by rearrangement, and from 1-(pentafluoroethyl)bicyclo[2.1.1]hexan-2-one (51) by ring expansion. Arenesulfonates and diazonium ions were used to generate the 2-norpinyl cations. – Electron acceptors in the α position of 2-norpinyl substrates promote the norpinyl→norbornyl rearrangement. Internal return of the counterion leads to endo-2-norbornyl sulfonates, often without formation of the analogous alcohols, i.e., the destabilized norpinyl cations do not escape from tight ion pairs. Electron acceptors in the β (bridgehead) position favor displacement and elimination processes with retention of the norpinyl structure while the norpinylnorbornyl rearrangement is inhibited, more strongly by β-C2F5 than by β-CN. The tendency to separate the positive charge from the electron acceptor explains the divergent effects of α and β substitution. – The kH/kα-CN and kH/kβ-CN rate ratios in the 2-norpinyl and 2-norbornyl series are virtually the same, and the stereoselectivity of the intervening carbocations is not significantly affected by electron-withdrawing substituents." @default.
- W2002156975 created "2016-06-24" @default.
- W2002156975 creator A5010185823 @default.
- W2002156975 creator A5021080832 @default.
- W2002156975 creator A5031692110 @default.
- W2002156975 creator A5048395836 @default.
- W2002156975 creator A5063405773 @default.
- W2002156975 creator A5067998184 @default.
- W2002156975 date "1995-10-01" @default.
- W2002156975 modified "2023-09-27" @default.
- W2002156975 title "Norpinyl-norbornyl rearrangements: Destabilized 2-norpinyl cations" @default.
- W2002156975 cites W1561428599 @default.
- W2002156975 cites W1964749382 @default.
- W2002156975 cites W1967374126 @default.
- W2002156975 cites W1972592275 @default.
- W2002156975 cites W1973076182 @default.
- W2002156975 cites W1973766634 @default.
- W2002156975 cites W1982036314 @default.
- W2002156975 cites W1982392105 @default.
- W2002156975 cites W1983679761 @default.
- W2002156975 cites W1984112317 @default.
- W2002156975 cites W1984986086 @default.
- W2002156975 cites W1989890726 @default.
- W2002156975 cites W1989922763 @default.
- W2002156975 cites W1996164608 @default.
- W2002156975 cites W1999126017 @default.
- W2002156975 cites W2000166520 @default.
- W2002156975 cites W2011464426 @default.
- W2002156975 cites W2013515079 @default.
- W2002156975 cites W2016951886 @default.
- W2002156975 cites W2022293635 @default.
- W2002156975 cites W2022513925 @default.
- W2002156975 cites W2023084018 @default.
- W2002156975 cites W2032851370 @default.
- W2002156975 cites W2033708481 @default.
- W2002156975 cites W2034361811 @default.
- W2002156975 cites W2036013317 @default.
- W2002156975 cites W2045611380 @default.
- W2002156975 cites W2049441085 @default.
- W2002156975 cites W2051044248 @default.
- W2002156975 cites W2051875318 @default.
- W2002156975 cites W2057164975 @default.
- W2002156975 cites W2063468514 @default.
- W2002156975 cites W2067426666 @default.
- W2002156975 cites W2073391937 @default.
- W2002156975 cites W2082861694 @default.
- W2002156975 cites W2084465741 @default.
- W2002156975 cites W2086138834 @default.
- W2002156975 cites W2088047991 @default.
- W2002156975 cites W2096268985 @default.
- W2002156975 cites W2139663789 @default.
- W2002156975 cites W2141152361 @default.
- W2002156975 cites W2150544105 @default.
- W2002156975 cites W2318402313 @default.
- W2002156975 cites W2320261999 @default.
- W2002156975 cites W2324042243 @default.
- W2002156975 cites W2328190066 @default.
- W2002156975 cites W2486917906 @default.
- W2002156975 cites W2912373437 @default.
- W2002156975 cites W2949614732 @default.
- W2002156975 cites W2949753018 @default.
- W2002156975 cites W2950096171 @default.
- W2002156975 cites W3005201304 @default.
- W2002156975 cites W4210960007 @default.
- W2002156975 cites W4246441921 @default.
- W2002156975 doi "https://doi.org/10.1002/jlac.1995199510244" @default.
- W2002156975 hasPublicationYear "1995" @default.
- W2002156975 type Work @default.
- W2002156975 sameAs 2002156975 @default.
- W2002156975 citedByCount "3" @default.
- W2002156975 countsByYear W20021569752015 @default.
- W2002156975 crossrefType "journal-article" @default.
- W2002156975 hasAuthorship W2002156975A5010185823 @default.
- W2002156975 hasAuthorship W2002156975A5021080832 @default.
- W2002156975 hasAuthorship W2002156975A5031692110 @default.
- W2002156975 hasAuthorship W2002156975A5048395836 @default.
- W2002156975 hasAuthorship W2002156975A5063405773 @default.
- W2002156975 hasAuthorship W2002156975A5067998184 @default.
- W2002156975 hasConcept C109057382 @default.
- W2002156975 hasConcept C145148216 @default.
- W2002156975 hasConcept C155647269 @default.
- W2002156975 hasConcept C178790620 @default.
- W2002156975 hasConcept C180827041 @default.
- W2002156975 hasConcept C185592680 @default.
- W2002156975 hasConcept C24961977 @default.
- W2002156975 hasConcept C2780378348 @default.
- W2002156975 hasConcept C2900893 @default.
- W2002156975 hasConcept C34814092 @default.
- W2002156975 hasConcept C71240020 @default.
- W2002156975 hasConcept C75473681 @default.
- W2002156975 hasConceptScore W2002156975C109057382 @default.
- W2002156975 hasConceptScore W2002156975C145148216 @default.
- W2002156975 hasConceptScore W2002156975C155647269 @default.
- W2002156975 hasConceptScore W2002156975C178790620 @default.
- W2002156975 hasConceptScore W2002156975C180827041 @default.
- W2002156975 hasConceptScore W2002156975C185592680 @default.
- W2002156975 hasConceptScore W2002156975C24961977 @default.
- W2002156975 hasConceptScore W2002156975C2780378348 @default.