1979
DOI: 10.1021/ja00515a002
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Hyperconjugation and homohyperconjugation in the 1-adamantyl cation. Qualitative models for .gamma.-deuterium isotope effects

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Cited by 35 publications
(17 citation statements)
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“…1-Adamantanemethylamine was originally prepared by reduction of 1-adamantanecarbonitrile with LiAlH 4 and recrystalized from hexane; subsequent samples were obtained from Aldrich Chemical Co. All other compounds were purchased from Aldrich Chemical Co. and used without further purification. 1-AdBr-3 d 1 was prepared according to a known procedure …”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…1-Adamantanemethylamine was originally prepared by reduction of 1-adamantanecarbonitrile with LiAlH 4 and recrystalized from hexane; subsequent samples were obtained from Aldrich Chemical Co. All other compounds were purchased from Aldrich Chemical Co. and used without further purification. 1-AdBr-3 d 1 was prepared according to a known procedure …”
Section: Methodsmentioning
confidence: 99%
“…In solution, both 1Ad • and 2Ad • have been generated and characterized by ESR. 3 The 1Ad + can be prepared by treating adamantane with super acids, and the ions so produced have been well-characterized by 1 H and 13 C nuclear magnetic resonance spectroscopies; it is believed that the ions retain their tricyclic structure. 4 The isomerization of 1Ad + to generate 2Ad + , by a 1,2-hydride shift, is strongly inhibited in the ionic species because the vacant orbital at the carbon center and the orbital of the migrating group are rigidly held in a conformation unfavorable for the Hmigration.…”
Section: Introductionmentioning
confidence: 99%
“…Thus, only the 2-norbornyl cation is observed by NMR upon ionization of 1-chloronorbornane in an SbF 5 /SO 2 system at low temperatures . In contrast with this, the 1-adamantyl cation 16(+) (see Table ) is readily prepared in solution. 15b, The cation 16(+) is stabilized by carbon−carbon hyperconjugation (σ-participation) . The carbon−hydrogen hyperconjugation is not favorable in this system because it would violate Bredt's rule 15b.…”
Section: Introductionmentioning
confidence: 95%
“…10 Further studies suggested that resonance stabilization, such as in Figure 1b, represents a clear picture of a C-C hyperconjugation effect. 11 Figure 1 (a) The empty 'p' orbital of the carbocation is stabilized with other three sp 3 bridgehead C-H bonds. 10 (b) The 1-adamantyl carbocation center is much more stable than other tertiary carbocations due to these resonance stabilizations.…”
mentioning
confidence: 99%
“…Structures i, ii, and iii are equivalent. 11 Our laboratory needed an efficient and simple synthetic method for 1-adamantylhydrazine, because it is a mandatory precursor for the synthesis of 1-adamantyl-substituted pyrazolylthioureas with NNSN-motif. 12 This class of novel antibiotics is activated by copper(I) in activated phagosomes 13 and is very effective against Gram-positive bacteria, such as MRSA (methicillin-resistant Staphylococcus aureus).…”
mentioning
confidence: 99%