ChemInform Abstract: SYNTHESE 2‐SUBSTITUIERTER ADAMANTANE AUS ADAMANTAN‐2‐SPIRO‐3′‐DIAZIRIN

Isaev, S. D.; Yurchenko, A. G.; Murzinova, Z. N.; Stepanov, F. N.; Kolyada, G. G.; Новиков, С. С.

doi:10.1002/chin.197436175

Cited by 4 publications

(5 citation statements)

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“…The absorption between 300 and 400 nm (Figure 2) allows rapid photolysis of the reagent at wavelengths that are generally harmless to biological systems (Knowles, 1972;Bayley & Knowles, 1977). The photogenerated carbene is known to be highly reactive (Isaev et al, 1974;Bayley & Knowles, 1978b) and is expected to be of low polarity, like its precursor.…”

Section: Discussionmentioning

confidence: 99%

Photogenerated reagents for membranes: selective labeling of intrinsic membrane proteins in the human erythrocyte membrane

Bayley¹,

Knowles²

1980

Biochemistry

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1-[3H]Spiro[adamantane-4,4'-diazirine], a lipophilic, photoactivatable reagent designed to label those segments of intrinsic proteins that lie within the lipid bilayer of biological membranes, has been evaluated. The reagent labels the intrinsic proteins of human erythrocyte membranes far more heavily than it labels the extrinsic proteins. This result, together with a detailed analysis of the label distribution in several well-characterized membrane proteins [Goldman, D.W., Pober, J.S., White, J., & Bayley, H. (1979) Nature (London) 280, 841], demonstrates that labeling with adamantanediazirine is a convenient and rapid method both for distinguishing intrinsic from extrinsic membrane proteins and for locating within intrinsic proteins those amino acid residues that are in contact with the hydrocarbon core of the lipid bilayer.

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Section: Discussionmentioning

confidence: 99%

Photogenerated reagents for membranes: selective labeling of intrinsic membrane proteins in the human erythrocyte membrane

Bayley¹,

Knowles²

1980

Biochemistry

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“…Twistane (II) was synthesized according to a 11-step scheme from cyclohexa-1,3-diene and ethyl acrylate [32], noradamantane (III) was prepared in 4 steps from protoadamantanone [33], cubane (IV) was obtained by an improved procedure from cyclopentanone [34], 2,4-dehydroadamantane (V) was synthesized by pyrolysis of spiro[adamantane-2,3′-diazirine] as described in [35], and protoadamantane (VI) was prepared in 4 steps [36] from commercially available adamantan-1-ol. Lithium tetrafluoroborate (Aldrich) was used without additional purification.…”

Section: Methodsmentioning

confidence: 99%

Comparative theoretical and experimental analysis of hydrocarbon σ-radical cations

et al. 2011

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The structures of σ-radical cations formed by ionization of adamantane, twistane, noradamantane, cubane, 2,4-dehydroadamantane, and protoadamantane were optimized at the B3LYP, B3LYP-D, M06-2X, B3PW91, and MP2 levels of theory using 6-31G(d), 6-311+G(d,p), 6-311+G(3df,2p), cc-PVDZ, and cc-PVTZ basis sets. On the whole, single-configuration approximations consistently describe the structure and transformations of the examined σ-radical cations. The best correlations (r = 0.97-0.98) between the calculated adiabatic ionization potentials and experimental oxidation (anodic) potentials of hydrocarbons were obtained in terms of B3PW91 approximation.Radical cations are formed as intermediates in a number of important natural processes. They are responsible for repair of damaged DNA [1], antioxidant properties of carotenoids [2], photosynthesis [3,4], and visual process [5]; radical cations are also formed in chemical reactions occurring in atmosphere [6]. Radical cations are generated during important preparative oxidative transformations, and their study is necessary for understanding fundamental reaction mechanisms [7,8]. Detection and structural analysis of hydrocarbon radical cations are limited by the existing physical methods. Recording of their electronic spectra is possible when characteristic absorption bands are intrinsic to radical cations [9]. Magnetic resonance methods are more informative, but their application is limited by short lifetime of radical cation intermediates [10]. Unfortunately, most available methods are almost inapplicable to extremely unstable hydrocarbon σ-radical cations, and only a few examples of such studies have been reported [11].On the other hand, modern computational procedures make it possible to predict the structure and behavior of hydrocarbon σ-radical cations, though the results of theoretical calculations sometimes do not agree with the experimental data because of dynamic effects. For example, DFT quantum-chemical calculations predicted an energy minimum for methane radical cation having C 2v symmetry [12], whereas analysis of the ESR spectrum recorded in neon matrix at 4 K indicated equivalence of all four protons [13].We previously studied the structure and transformations of radical cations derived from adamantane and its alkyl derivatives [14], cubane [15], protoadamantane [16], homoadamantane [17], propellanes [18], and rotanes [19] in terms of the density functional theory (DFT) with the use of popular B3LYP functional. Although in some cases good correlations between the calculated (B3LYP) and experimental data were observed, in particular for diamondoids [20], the problem related to applicability of various theoretical approaches to hydrocarbon σ-radical cations and improvement of their quality remains important. Among other factors, the reason is that standard DFT approximations tend to localize charge and spin density in radical cations [21].Furthermore, during the past 5 years, appropriateness of DFT methods (especially of B3LYP) for the calculation of even simp...

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“…Exceptions occur when intramolecular processes are slowed by the formation of highly strained or energetic products such as anti-Bredt olefins, multicyclic alkanes, or allenes. Apposite carbenes include 7-norbornanylidene, cyclopropylidene, homocub-9-ylidene, and adamantanylidene. , …”

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confidence: 99%

“…Among these, adamantanylidene ( 1 , Ad) exhibits a robust and well-developed intermolecular chemistry. − Long ago, we reported that photolysis of aziadamantane ( 2 ) afforded Ad, which added to various alkenes to give the derivative cyclopropanes ( 3 ) …”

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confidence: 99%

The Nucleophilicity of a Dialkylcarbene: Unusual Activation Parameters for Additions of Adamantanylidene to Simple Alkenes

2014

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Computational and experimental results demonstrate that adamantanylidene (1) behaves as a highly reactive nucleophile toward common alkenes. It is the only known saturated nucleophilic carbene that lacks direct or vinylogous heteroatomic substitution. The activation energy and enthalpy for addition of 1 to methyl acrylate are the most negative values yet encountered in any carbene-alkene addition.

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ChemInform Abstract: SYNTHESE 2‐SUBSTITUIERTER ADAMANTANE AUS ADAMANTAN‐2‐SPIRO‐3′‐DIAZIRIN

Abstract: Das bei der Thermolyse des Diazirins (I) in Cyclohexan bei 200‐220°C entstehende Carben reagiert mit der Ausgangsverbindung zum Azin (II), mit dem Lösungsmittel zum Cyclohexyladamantan (IV); außerdem entstehen geringe Mengen des Dehydroadamantans (III).

Cited by 4 publications

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Photogenerated reagents for membranes: selective labeling of intrinsic membrane proteins in the human erythrocyte membrane

Photogenerated reagents for membranes: selective labeling of intrinsic membrane proteins in the human erythrocyte membrane

Comparative theoretical and experimental analysis of hydrocarbon σ-radical cations

The Nucleophilicity of a Dialkylcarbene: Unusual Activation Parameters for Additions of Adamantanylidene to Simple Alkenes

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