Chemistry of nitrenium ions. XXVI. Neighboring group participation by bridgehead nitrogen in bridged polycyclic systems

Gassman, Paul G.; Cryberg, Richard L.; Shudo, Koichi

doi:10.1021/ja00776a067

Cited by 18 publications

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“…Thus, the nitrogen adjacent to the bridgehead carbon produces a rate acceleration of nearly 2 X 105. This result compares nicely with a recent observation by Wiseman113 and coworkers who reported that l-chloro-9-methyl-9-azabicyclo[3.3.1]nonane (10) solvolyzed nearly ten million times faster than its carbocyclic counterpart, 1-chlorobicyclo[3.3.1]nonane (11).…”

Section: Discussionsupporting

confidence: 90%

Participation by adjacent nitrogen during solvolysis of bridgehead halide, 1-chloro-3,3-dimethyl-2-azabicyclo[2.2.2]octane

Wnuk¹,

Kovacic²

1975

J. Am. Chem. Soc.

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Section: Discussionsupporting

confidence: 90%

Participation by adjacent nitrogen during solvolysis of bridgehead halide, 1-chloro-3,3-dimethyl-2-azabicyclo[2.2.2]octane

Wnuk¹,

Kovacic²

1975

J. Am. Chem. Soc.

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“…All the hydride migrations in mono-substituted norbornyl systems and related bicyclic structures are intramolecular. 30–32 These results strongly support the hypothesis of pair of front-face “equatorial” hydride shifts via the bridgehead position rather than the nonstereospecific 6,2,1 shift for which there is no evidence and has been assumed.…”

Section: Discussionsupporting

confidence: 72%

1-Norbornyl cation may be in equilibrium with 2-norbornyl cation

Mamantov

2019

Progress in Reaction Kinetics and Mechanism

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New 1H and 13C NMR 400 MHZ spectra of the 2-Nb cation under stable ion conditions, for example, in SbF5/SO2F2/SO2ClF, −80 oC, show besides the usual 1H NMR resonances at δ 4.93, 2.82, 1.85, the never before seen singlet, δ 9.63, and doublet, δ 2.97 (J2,6 = 16.6 Hz), ratio 1.00 : 1.07, proposed to be due to resonance-stabilized bridgehead 1-Nb cationic enantiomers in equilibrium with 2-Nb cation. The corresponding 13C proton-coupled NMR spectrum, −80 oC, has a C3,5,7 triplet, δ 30.45, J(CH) = 139.14 Hz, and C4 doublet, δ 37.7, J(CH) = 154.54 Hz. The C1,2,6 absorption, δ 91.04 is relatively broad, whereas previously, at −70 oC, it was a pentuplet. The 13C proton-decoupled spectrum at −80 oC shows the C4 doublet and C3,5,7 triplet collapsed to a singlet, but the C1,2,6 resonance is still broad. Analyses support the slowing exchange between resonance stabilized enantiomeric 2-cations at ≤ –159 oC. Some future studies are proposed.

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Methoden zur Herstellung von Brückenkopf‐Olefinen

Keese

1975

Angewandte Chemie

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Bruckenkopf-Olefinen wird seit ungefahr acht Jahren ein sturmisch wachsendes Interesse entgegengebracht. In Anbetracht ihrer Bedeutung fur die Stereochemie yon Alkenen, das Studium einiger Reaktionsmechanismen und die Natur der Doppelbindung ist eine umfassende Erforschung dieses Strukturtyps envunscht. Bruckenkopf-Olefine sind Bindeglieder zwischen Olefinen im Grundzustand und Spezies, die bei der Desaktivierung photochemisch angeregter Alkene und Cycloalkene entstehen konnen und tragen zum Verstandnis der strukturellen Verhaltnisse der cis-trans-Isomerisierung von Alkenen bei.

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Chemistry of nitrenium ions. XXVI. Neighboring group participation by bridgehead nitrogen in bridged polycyclic systems

Cited by 18 publications

References 0 publications

Participation by adjacent nitrogen during solvolysis of bridgehead halide, 1-chloro-3,3-dimethyl-2-azabicyclo[2.2.2]octane

Participation by adjacent nitrogen during solvolysis of bridgehead halide, 1-chloro-3,3-dimethyl-2-azabicyclo[2.2.2]octane

1-Norbornyl cation may be in equilibrium with 2-norbornyl cation

Methoden zur Herstellung von Brückenkopf‐Olefinen

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