22188-03-0Relevant articles and documents
Trans-Selective and Switchable Arene Hydrogenation of Phenol Derivatives
Bergander, Klaus,Glorius, Frank,Heusler, Arne,Wollenburg, Marco
, p. 11365 - 11370 (2020/11/24)
A trans-selective arene hydrogenation of abundant phenol derivatives catalyzed by a commercially available heterogeneous palladium catalyst is reported. The described method tolerates a variety of functional groups and provides access to a broad scope of trans-configurated cyclohexanols as potential building blocks for life sciences and beyond in a one-step procedure. The transformation is strategically important because arene hydrogenation preferentially delivers the opposite cis-isomers. The diastereoselectivity of the phenol hydrogenation can be switched to the cis-isomers by employing rhodium-based catalysts. Moreover, a protocol for the chemoselective hydrogenation of phenols to cyclohexanones was developed.
COMPOUNDS COMPRISING N-METHYL-2-PYRIDONE, AND PHARMACEUTICALLY ACCEPTABLE SALTS
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Page/Page column 73, (2020/12/30)
The present invention concerns compounds comprising N-methyl-2-pyridone, and pharmaceutically-acceptable salts and compositions of such compounds. Such compounds are useful in anti-inflammatory and anti-cancer therapies. Therefore, the present invention also concerns such compounds for use as medicaments, particularly for the treatment of inflammatory diseases and oncology.
CYCLOALKYL CONTAINING THIENOPYRIMIDINES FOR PHARMACEUTICAL COMPOSITIONS
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, (2011/10/02)
The present invention relates to novel thienopyrimidine compounds of general formula pharmaceutical compositions comprising these compounds and their therapeutic use for the prophylaxis and/or treatment of diseases which can be influenced by the inhibition of the kinase activity of Mnk1 and/or Mnk2 (Mnk2a or Mnk2b) and/or variants thereof.
Hydrogen bonding lowers intrinsic nucleophilicity of solvated nucleophiles
Chen, Xin,Brauman, John I.
scheme or table, p. 15038 - 15046 (2009/03/12)
The relationship between nucleophilicity and the structure/environment of the nucleophile is of fundamental importance in organic chemistry. In this work, we have measured nucleophilicities of a series of substituted alkoxides in the gas phase. The functional group substitutions affect the nucleophiles through ion-dipole, ion-induced dipole interactions and through hydrogen bonding whenever structurally possible. This set of alkoxides serves as an ideal model system for studying nucleophiles under microsolvation settings. Marcus theory was applied to analyze the results. Using Marcus theory, we separate nucleophilicity into two independent components, an intrinsic nucleophilicity and a thermodynamic driving force determined solely by the overall reaction exothermicity. It is found that the apparent nucleophilicities of the substituted alkoxides are always much lower than those of the unsubstituted ones. However, ion-dipole, ion-induced dipole interactions, by themselves, do not significantly affect the intrinsic nucleophilicity; the decrease in the apparent nucleophilicity results from a weaker thermodynamic driving force. On the other hand, hydrogen bonding not only stabilizes the nucleophile but also increases the intrinsic barrier height by 3 to ～4 kcal mol-1. In this regard, the hydrogen bond is not acting as a perturbation in the sense of an external dipole but more directly affects the electronic structure and reactivity of the nucleophilic alkoxide. This finding offers a deeper insight into the solvation effect on nucleophilicity, such as the remarkably lower reactivities in nucleophilic substitution reactions in protic solvents than in aprotic solvents.
The mechanism of methanol loss from the (M-H) ions of cis- And trans-4-methoxycyclohexanol. the application of experiment and theory in concert
Dua, Suresh,Buntine, Mark A.,Raftery, Mark J.,Eichinger, Peter C. H.,Bowie, John H.
, p. 2489 - 2496 (2007/10/03)
Deprotonation of cis- and trans-4-methoxycyclohexanol by HO- in the ion source of a mass spectrometer yields the (M - H)- alkoxide ions exclusively. Both of these ions, on collisional activation, form MeO-, MeO-(H2O) and eliminate MeOH. The loss of methanol forms the base peak of the spectrum, and the structure of this daughter anion is shown to be the alkoxide ion from cyclohex-3-enol for both isomers. Evidence (based on product ion, deuterium labelling and AMI semiempirical computational studies) indicates that the loss of methanol from the trans isomer proceeds by an internal SN2 cyclisation of O- at the four position (through a 1,4-epoxycyclohexane species) followed by 3,4 elimination. A similar sequence may occur for the cis-isomer, but in this case the process is not as energetically favourable as that for the trans isomer.
